CN114437412A - Preparation method of rubber anti-aging material - Google Patents
Preparation method of rubber anti-aging material Download PDFInfo
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- CN114437412A CN114437412A CN202210184035.XA CN202210184035A CN114437412A CN 114437412 A CN114437412 A CN 114437412A CN 202210184035 A CN202210184035 A CN 202210184035A CN 114437412 A CN114437412 A CN 114437412A
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- 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
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Processes Of Treating Macromolecular Substances (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
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Abstract
The invention discloses a preparation method of a rubber anti-aging material, which comprises the following specific steps: s1, placing the silicon oxide microporous material, the artificial zeolite and the bentonite into a ball mill, grinding and stirring to obtain mixed powder, and drying in vacuum to obtain the composite microporous material; s2, preparing an anti-aging material acetone solution, and adding the composite microporous material obtained in the step S1 into the anti-aging material acetone solution to obtain a composite microporous material mixed solution loaded with the anti-aging material; and S3, adding a silane coupling agent into the mixed solution, performing ultrasonic mixing for 5-10min, performing constant-temperature reaction in a constant-temperature reaction kettle for 2-3h, and performing centrifugal vacuum drying to obtain the modified slow-release rubber anti-aging material. The invention takes the microporous material obtained by compounding three microporous materials as a matrix, uses a concentrated solution filling method to fill and load the anti-aging material in the micropores of the composite microporous material, and carries out surface modification on the microporous material loaded with the anti-aging material, thereby improving the dispersibility of the microporous material in a rubber body and further improving the mechanical property and the aging resistance of the rubber.
Description
Technical Field
The invention belongs to the field of rubber additives, and particularly relates to a preparation method of a rubber anti-aging material, belonging to the field of rubber additives.
Background
The rubber material belongs to strategic materials, plays an important role in the national defense industry, almost all types of projects can not leave rubber products, and the rubber material is particularly inexhaustible in application to modern warplanes, naval vessels, rockets and the like. The quality is the basis of military industry, the quality of the product is good and bad, the service life is long, the relationship is important, the quality of the rubber product is the same, but the aging phenomenon of the rubber material seriously hinders or limits the application of the rubber material.
However, the small molecule anti-aging material can migrate among rubber macromolecular networks to be enriched on the surface of the rubber product, so that the phenomenon of 'blooming' is caused. Therefore, the parts of the anti-aging materials in the rubber formula are strictly limited, and the highest addition parts of different anti-aging materials are different.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a preparation method of a rubber anti-aging material, which is characterized in that a microporous material obtained by compounding three microporous materials is used as a matrix, an anti-aging agent is filled and loaded in micropores of the composite microporous material by a concentrated solution filling method, and the surface of the microporous material loaded with the anti-aging agent is modified, so that the dispersibility of the microporous material in a rubber body is improved, and the mechanical property and the anti-aging property of rubber are further improved.
The invention mainly adopts the technical scheme that:
a preparation method of a rubber anti-aging material comprises the following specific steps:
s1: placing 65-85 wt% of silicon oxide microporous material, 10-35 wt% of artificial zeolite and 0-15 wt% of bentonite in a ball mill, grinding and stirring for 10-30 min to obtain mixed powder, adding the mixed powder into absolute alcohol, performing ultrasonic dispersion for 0.5-2h under 200W power, and performing vacuum drying at 30-45 ℃ to obtain the composite microporous material;
s2: preparing an anti-aging agent acetone solution with a certain concentration, adding the composite microporous material obtained in the step S1 into the anti-aging agent acetone solution in proportion, oscillating for 1-2h by using 100W ultrasonic waves, vacuumizing, keeping the vacuum environment for 10-40 min, and keeping the vacuum environment for 5-30 min at normal pressure to obtain an anti-aging agent-loaded composite microporous material mixed solution;
s3: and (4) adding a certain amount of silane coupling agent into the mixed solution obtained in the step S2, performing ultrasonic mixing for 5-10min, performing constant-temperature reaction in a constant-temperature reaction kettle for 2-3h, and performing centrifugal vacuum drying to obtain the modified slow-release rubber anti-aging material.
Preferably, the particle size of the silicon oxide microporous material in the step S1 is 100-1 μm, the pore diameter is 0.3-1.2nm, the particle size of the artificial zeolite is 1-20nm, the pore diameter is 0.2-1.5nm, and the particle size of the bentonite is 10-50 nm, and the pore diameter is 0.5-2 nm.
Preferably, in step S2, the antioxidant is one or more of antioxidant 4020, antioxidant IPPD, antioxidant 4010, or antioxidant D.
Preferably, the concentration of the acetone solution of the anti-aging agent in the step S2 is 2-25 g/L.
Preferably, the mixing ratio of the composite microporous material to the anti-aging agent in the step S2 is 2:1-1: 2.
Preferably, in the step S3, the adding amount of the silane coupling agent is 30-50% of the composite microporous material by mass.
Preferably, in the step S3, the isothermal reaction temperature of the isothermal reaction kettle is 80-95 ℃.
Has the advantages that: the invention provides a preparation method of a rubber anti-aging material, which has the following advantages:
1. the anti-aging agent is loaded in the micropore gap by utilizing the adsorption effect of the micropore structure of the composite micropore material, so that the anti-aging agent is controlled and slowly released, the dosage of the anti-aging material in the rubber formula can be increased on the premise of not causing blooming, and the anti-aging new performance of the rubber is further improved.
2. The microporous material obtained by compounding various microporous materials can combine the adsorption performance of various materials, simultaneously can improve the dispersion of the microporous material and reduce the agglomeration phenomenon, and the microporous material can also be used as a reinforcing filler of a rubber matrix and jointly acts on the rubber matrix with an anti-aging agent.
3. The surface modification is carried out on the microporous material loaded with the anti-aging agent, so that the dispersibility of the microporous material can be improved, and the reinforcing effect of the microporous material on rubber is improved.
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.
Example 1
A preparation method of a rubber anti-aging material comprises the following specific steps:
s1, putting 65 wt% of silicon oxide microporous material (the granularity is 100 nm and the aperture is 0.8nm), 25 wt% of artificial zeolite (the granularity is 10nm and the aperture is 0.8nm) and 10 wt% of bentonite (the granularity is 20nm and the aperture is 0.8nm) into a ball mill, grinding and stirring for 20min to obtain mixed powder, adding the mixed powder into absolute ethyl alcohol, performing ultrasonic dispersion for 1h under 200W power, and then performing vacuum drying at 45 ℃ to obtain the composite microporous material;
s2, preparing an anti-aging agent acetone solution with a certain concentration (25 g/L), adding the composite microporous material obtained in the step S1 into the anti-aging agent acetone solution in a ratio (2: 1), oscillating the solution for 2 hours by adopting 100W ultrasonic waves, vacuumizing the solution, keeping the solution for 40min in a vacuum environment, and keeping the solution for 30min at normal pressure to obtain an anti-aging agent-loaded composite microporous material mixed solution;
s3, adding a certain amount of silane coupling agent (KH550, 30%) into the mixed solution obtained in the step S2, performing ultrasonic mixing for 10min, performing constant-temperature reaction in a constant-temperature reaction kettle for 2h, and performing centrifugal vacuum drying to obtain the modified slow-release rubber anti-aging material.
Example 2
A preparation method of a rubber anti-aging material comprises the following specific steps:
s1, putting 70 wt% of silicon oxide microporous material (the granularity is 100 nm and the aperture is 0.8nm), 15 wt% of artificial zeolite (the granularity is 10nm and the aperture is 0.8nm) and 15 wt% of bentonite (the granularity is 20nm and the aperture is 0.8nm) into a ball mill, grinding and stirring for 20min to obtain mixed powder, then adding the mixed powder into absolute ethyl alcohol, performing ultrasonic dispersion for 1h under 200W power, and performing vacuum drying at 45 ℃ to obtain the composite microporous material;
s2, preparing an anti-aging agent acetone solution with a certain concentration (25 g/L), adding the composite microporous material obtained in the step S1 into the anti-aging agent acetone solution in a ratio (1: 1), oscillating the solution for 2 hours by adopting 100W ultrasonic waves, vacuumizing the solution, keeping the solution for 40min in a vacuum environment, and keeping the solution for 30min at normal pressure to obtain an anti-aging agent-loaded composite microporous material mixed solution;
s3, adding a certain amount of silane coupling agent ((KH 550, 40%)) into the mixed solution obtained in the step S2, performing ultrasonic mixing for 10min, performing constant-temperature reaction in a constant-temperature reaction kettle for 3h, and performing centrifugal vacuum drying to obtain the modified slow-release rubber anti-aging material.
Example 3
A preparation method of a rubber anti-aging material comprises the following specific steps:
s1, putting 85 wt% of silicon oxide microporous material (the granularity is 100 nm, and the aperture is 0.8nm), 10 wt% of artificial zeolite (the granularity is 10nm, and the aperture is 0.8nm), and 5 wt% of bentonite (the granularity is 20nm, and the aperture is 0.8nm) into a ball mill, grinding and stirring for 20min to obtain mixed powder, adding the mixed powder into absolute alcohol, performing ultrasonic dispersion at 200W for 1h, and performing vacuum drying at 45 ℃ to obtain the composite microporous material;
s2, preparing an anti-aging agent acetone solution with a certain concentration (25 g/L), adding the composite microporous material obtained in the step S1 into the anti-aging agent acetone solution in a ratio (1: 2), oscillating the solution for 2 hours by adopting 100W ultrasonic waves, vacuumizing the solution, keeping the solution for 40min in a vacuum environment, and keeping the solution for 30min at normal pressure to obtain an anti-aging agent-loaded composite microporous material mixed solution;
s3, adding a certain amount of silane coupling agent (KH550, 50%) into the mixed solution obtained in the step S2, carrying out ultrasonic mixing for 5-10min, carrying out constant-temperature reaction in a constant-temperature reaction kettle for 2-3h, and carrying out centrifugal vacuum drying to obtain the modified slow-release rubber anti-aging material.
Examples 1, 2 and 3 and ordinary antioxidant 4020 were kneaded according to the compounding recipe shown in table 1 to obtain sample 1, sample 2, sample 3 and sample 4, respectively.
Table 1: the addition amount of each component in the mixing formula
The rubber materials obtained by mixing the above samples 1, 2, 3 and 4 were subjected to physical and mechanical property tests before aging and after aging (100 ℃ C.. times.7 d) according to the national standards.
Weather aging resistance test method: taking the same standard sample, cutting the same standard sample into equal 3 pieces according to the length direction of the sample, wherein the length direction of the sample is vertical to the rolling and extruding directions, folding the test piece according to 360 degrees, fixing the same part of the test piece, then placing the test piece at the same position in the sunward direction, and observing the surface aging condition of the test piece after two months. The test results are specifically shown in table 2.
TABLE 2 test results of mechanical properties and thermal aging resistance of each sample
The following conclusions can be drawn from the above experimental results:
1) the physical and mechanical properties of the rubber material added with the modified anti-aging material are better than those of the rubber material added with the common anti-aging agent 4020.
2) The rubber material added with a large amount of modified anti-aging materials still has no cracking and blooming phenomena after the weather-resistant aging test for two months, and the rubber material added with the conventional anti-aging agent 4020 has the phenomena of whitening, yellowing and cracking after the weather-resistant aging test for 1 month. The addition amount of the anti-aging material in the formula is far higher than that of the conventional anti-aging agent (the conventional amount is 1-2 parts), but the anti-aging material realizes the slow release effect of the anti-aging agent by adopting the microporous material, so that the phenomenon of blooming caused by the addition of a large amount of anti-aging agent is avoided. It can also be seen from the above realization that the addition of an excess of the ordinary antioxidant 4020 takes only one week to produce a whitish and yellowish blooming phenomenon, while the present invention is completely free of cracking. Therefore, the modified anti-aging material of the invention not only improves the weather-aging cracking resistance of the rubber material, but also improves the discoloration resistance and the addition of the anti-aging material, thereby enhancing the anti-aging performance.
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 (7)
1. The preparation method of the rubber anti-aging material is characterized by comprising the following specific steps of:
s1, putting 65-85 wt% of silicon oxide microporous material, 10-35 wt% of artificial zeolite and 0-15 wt% of bentonite into a ball mill, grinding and stirring for 10-30 min to obtain mixed powder, adding the mixed powder into absolute alcohol, performing ultrasonic dispersion for 0.5-2h under 200W power, and performing vacuum drying at 30-45 ℃ to obtain the composite microporous material;
s2, preparing an anti-aging material acetone solution with a certain concentration, adding the composite microporous material obtained in the step S1 into the anti-aging material acetone solution in proportion, oscillating the solution for 1 to 2 hours by using 100W ultrasonic waves, vacuumizing the solution, keeping the solution for 10 to 40 minutes in a vacuum environment, and keeping the solution for 5 to 30 minutes at normal pressure to obtain a composite microporous material mixed solution loaded with the anti-aging material;
and S3, adding a certain amount of silane coupling agent into the mixed solution obtained in the step S2, carrying out ultrasonic mixing for 5-10min, carrying out constant-temperature reaction in a constant-temperature reaction kettle for 2-3h, and carrying out centrifugal vacuum drying to obtain the modified slow-release rubber anti-aging material.
2. The method for preparing the rubber anti-aging material according to claim 1, wherein the particle size of the microporous silica material in step S1 is 100 to 1 μm, the pore size is 0.3 to 1.2nm, the particle size of the artificial zeolite is 1 to 20nm, the pore size is 0.2 to 1.5nm, and the particle size of the bentonite is 10 to 50nm, and the pore size is 0.5 to 2 nm.
3. The method for preparing the rubber anti-aging material according to claim 1, wherein the anti-aging material in the step S2 is one or more of an anti-aging agent 4020, an anti-aging agent IPPD, an anti-aging agent 4010 or an anti-aging agent D.
4. The method for preparing a rubber anti-aging material according to claim 1, wherein the concentration of the acetone solution of the anti-aging material in the step S2 is 2 to 25 g/L.
5. The method for preparing the rubber anti-aging material according to claim 1, wherein the mixing ratio of the composite microporous material to the anti-aging material in the step S2 is 2:1-1: 2.
6. The method for preparing the rubber anti-aging material according to claim 1, wherein in the step S3, the adding amount of the silane coupling agent is 30-50% of the mass of the composite microporous material.
7. The method for preparing the rubber anti-aging material according to claim 1, wherein in the step S3, the constant temperature reaction temperature of the constant temperature reaction kettle is 80-95 ℃.
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| CN202210184035.XA CN114437412A (en) | 2022-02-28 | 2022-02-28 | Preparation method of rubber anti-aging material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013065768A1 (en) * | 2011-11-01 | 2013-05-10 | 住友化学株式会社 | Rubber anti-aging agent |
| CN103396592A (en) * | 2013-07-11 | 2013-11-20 | 华南理工大学 | Supported rubber anti-aging agent, as well as preparation method and application thereof |
| CN109627506A (en) * | 2018-12-22 | 2019-04-16 | 折伟 | A kind of preparation method of zeolite rubber composite material |
| CN111333914A (en) * | 2020-04-29 | 2020-06-26 | 江西宝弘纳米科技有限公司 | Slow-release anti-aging agent and preparation method and application thereof |
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- 2022-02-28 CN CN202210184035.XA patent/CN114437412A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013065768A1 (en) * | 2011-11-01 | 2013-05-10 | 住友化学株式会社 | Rubber anti-aging agent |
| CN103396592A (en) * | 2013-07-11 | 2013-11-20 | 华南理工大学 | Supported rubber anti-aging agent, as well as preparation method and application thereof |
| CN109627506A (en) * | 2018-12-22 | 2019-04-16 | 折伟 | A kind of preparation method of zeolite rubber composite material |
| CN111333914A (en) * | 2020-04-29 | 2020-06-26 | 江西宝弘纳米科技有限公司 | Slow-release anti-aging agent and preparation method and application thereof |
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