CN111925561A - Biomass rubber antioxidant and preparation method and application thereof - Google Patents
Biomass rubber antioxidant and preparation method and application thereof Download PDFInfo
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- C08K5/00—Use of organic ingredients
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Abstract
The invention discloses a biomass rubber antioxidant, a preparation method and application thereof, and belongs to the field of rubber antioxidants. The preparation method comprises the steps of adding the inorganic filler into the organic solvent, uniformly stirring, adding the biomass compound Tea Polyphenol (TP), and reacting for 4-10 hours at the temperature of 40-80 ℃. And finally, filtering, washing and drying the reaction product to constant weight to obtain the biomass rubber antioxidant. The biomass rubber antioxidant can remarkably improve the mechanical property and the anti-aging property of rubber, has multiple functions of a reinforcing agent, an interface modifier and the like, and can reduce blooming and migration of the rubber. The biomass rubber antioxidant can reduce or replace the usage amount of the traditional antioxidant in rubber, is a high-efficiency, multifunctional and environment-friendly rubber antioxidant aid, and has wide application prospect in the rubber industry.
Description
Technical Field
The invention relates to the field of rubber anti-aging agents, and particularly relates to a biomass rubber anti-aging agent, and a preparation method and application thereof.
Background
The aging of the rubber composite is mainly caused by thermal oxygen. The aging of the rubber composite material can be accelerated by the material under the conditions of high temperature, excessive oxygen, ultraviolet radiation and chemical substances, and the application of the rubber composite material is greatly limited. In order to prolong the service life of the rubber composite material, a rubber anti-aging agent is added into the rubber composite material to remove free radicals generated in a rubber matrix due to aging. Most of the rubber antioxidant auxiliaries are mainly low molecular weight organic compounds, however, the organic low molecular weight rubber antioxidant auxiliaries also have many disadvantages, such as low antioxidant efficiency, easy migration, easy volatilization at high temperature, and pollution to products and environment. With the continuous improvement of the use requirements of modern industry and national defense on rubber products, the prepared efficient, multifunctional and environment-friendly biomass rubber antioxidant replaces the traditional rubber antioxidant, reduces the use of the rubber antioxidant, and becomes the development trend of the rubber additive industry at present.
Disclosure of Invention
The invention aims to overcome the defects that the existing rubber anti-aging auxiliary agent has low aging efficiency, is easy to migrate in a rubber matrix, causes blooming, has single function and has certain harm to people and the environment in the preparation and use processes of the rubber anti-aging agent. Therefore, the invention provides the efficient, multifunctional and environment-friendly biomass rubber anti-aging agent and the preparation method and application thereof.
The purpose of the invention is realized by the following scheme.
A preparation method of a biomass rubber anti-aging agent is characterized in that biomass compound tea polyphenol is combined to the surface of an inorganic filler in a covalent bond mode through chemical reaction to obtain the biomass rubber anti-aging agent, and the preparation method comprises the following steps:
firstly, adding an inorganic filler into an organic solvent, and uniformly stirring and mixing to obtain a mixed solution;
secondly, adding biomass compound tea polyphenol into the mixed solution, and reacting at 40-80 ℃;
and thirdly, filtering, washing and drying a product obtained by the reaction to obtain the biomass rubber anti-aging agent.
Preferably, the inorganic filler is micro-or nano-scale inorganic particles.
Further preferably, the inorganic filler includes one or more of white carbon black, halloysite, nanocrystalline cellulose, montmorillonite, mica powder, attapulgite, diatomite, kaolin, carbon black, talcum powder and silicon powder.
Preferably, the organic solvent is one of ethanol, toluene, ethyl acetate and petroleum ether.
Preferably, the solid mass content of the inorganic filler in the mixed solution is 5 to 30 percent.
Preferably, the stirring and mixing time is 2-4 hours.
Preferably, the addition amount of the inorganic filler is 1-10 times of the mass of the tea polyphenol.
Preferably, the reaction time is 4-10 hours.
Taking biomass rubber antioxidant Silica-s-TP formed by biomass compound tea polyphenol and white carbon black as an example, the preparation principle is as follows:
in the above method, the biomass compound is Tea Polyphenol (TP). Tea polyphenols are water-soluble mixtures composed of typical condensed tannins, mainly comprising four catechins: epigallocatechin gallate (EGCG), Epigallocatechin (EGC), epicatechin gallate (ECG), Epicatechin (EC), wherein EGCG accounts for 50-60% of total amount of tea polyphenols.
The biomass rubber anti-aging agent prepared by the preparation method.
The biomass rubber antioxidant is applied to preparation of natural rubber and synthetic rubber composite materials.
The invention synthesizes the biomass rubber anti-aging agent taking inorganic filler as a carrier. The biomass rubber antioxidant can replace the traditional rubber antioxidant, and can effectively improve the thermal oxidation aging resistance and ultraviolet aging resistance of rubber. Meanwhile, the modified rubber can be used as an interface modifier of the filler, the interface combination of the filler and the rubber matrix is enhanced, the dispersion of the filler in the rubber matrix is improved, and the physical and mechanical properties of the rubber product are improved.
Compared with the prior art, the invention has the following advantages:
1. the biomass compound Tea Polyphenol (TP) in the biomass rubber antioxidant is also called plant polyphenol, is a secondary metabolite of phenols in plants, widely exists in skins, roots, leaves and fruits of the plants, has the content inferior to that of cellulose, hemicellulose and lignin in the biological world, and brings unique physicochemical properties to the biomass compound Tea Polyphenol (TP) due to the polyphenol structure of the biomass rubber antioxidant. Has wide source in nature and no pollution to the environment, thereby having better application prospect.
2. In the synthesis process of the biomass rubber antioxidant, the biomass compound Tea Polyphenol (TP) is grafted to the surface of the inorganic filler through a chemical reaction, so that the surface energy of the inorganic filler is reduced, the agglomeration in a rubber matrix is reduced, and the dispersion of the inorganic filler in the rubber matrix is enhanced.
3. The biomass compound Tea Polyphenol (TP) in the biomass rubber antioxidant is grafted to the surface of a micron or nano inorganic filler through a chemical reaction, so that the thermal stability of the material is improved, and the material has a better aging effect. In addition, it can also act as an interfacial modifier for the filler, enhancing the interfacial bonding of the inorganic filler to the rubber matrix, as compared to unmodified inorganic fillers.
4. The biomass rubber anti-aging agent further increases the molecular weight thereof and enhances the acting force between molecules through chemical reaction, so that the mobility resistance and the volatility resistance of the biomass rubber anti-aging agent are improved in the using process.
5. The preparation process of the biomass rubber antioxidant is simple, the separation process is simple, the solvent is low in toxicity and can be repeatedly utilized, and the preparation method is beneficial to cost reduction and industrial popularization.
Drawings
FIG. 1 is a graph showing an ultraviolet absorption spectrum of a biomass rubber antioxidant in example 1;
FIG. 2 is a graph showing the thermogravimetric loss of the biomass rubber antioxidant in example 1;
FIG. 3 is a graph of thermal oxygen aged crosslink density of the biomass rubber antioxidant of example 2;
FIG. 4 is a graph showing the thermo-oxidative aging tensile retention of the biomass rubber antioxidant in example 2;
FIG. 5 is a graph showing retention of thermal oxidative aging elongation at break of the biomass rubber antioxidant of example 2;
FIG. 6 is a graph of thermal oxygen aged crosslink density of the biomass rubber antioxidant of example 3;
FIG. 7 is a graph showing the retention of tensile elongation after thermal oxidative aging of the biomass rubber antioxidant of example 3;
FIG. 8 is a graph showing retention of elongation at break after thermal oxidative aging of the biomass rubber antioxidant in example 3.
Detailed Description
For a better description and understanding of the invention, reference is made to the following description, taken in connection with the accompanying drawings, wherein the scope of the invention is not limited to the embodiments shown.
Example 1
Dissolving 10g of white carbon black (Silica) into 200ml of absolute ethyl alcohol, stirring for 2h at room temperature to fully mix the solution, adding 10g of Tea Polyphenol (TP) into the mixed solution, reacting for 4h at 40 ℃, washing the obtained product with absolute ethyl alcohol, centrifuging, and drying to constant weight to obtain the final product.
The obtained biomass rubber antioxidant is named as Silica-s-TP. The ultraviolet absorption spectrum (see FIG. 1) shows that at 220nm-1Is represented by pi-pi of benzene ring structure in Tea Polyphenol (TP)*At 270nm-1Is a conjugated structure n-pi in a Tea Polyphenol (TP) benzene ring structure*And in Silica-s-TP likewise 220nm-1And 270nm-1And (3) a peak, which indicates that the Tea Polyphenol (TP) is successfully loaded on the surface of the silicon dioxide through chemical reaction and silicon hydroxyl on the surface of the silicon dioxide to synthesize a target product, and thermogravimetric analysis (shown in figure 2) shows that the loading mass fraction of the tea polyphenol in the Silica-s-TP is 26.66%.
The basic formulation of a styrene-butadiene rubber composite prepared with the product Silica-s-TP is shown in Table 1 (unit: parts by weight phr).
Table 2 shows the mechanical properties of styrene butadiene rubber composite materials prepared by using the biomass rubber antioxidant silica-s-TP, and it can be seen from the table that the addition of the biomass rubber antioxidant silica-s-TP to the rubber matrix can improve the mechanical properties of the rubber composite materials, such as tensile strength, stress at definite elongation, tear strength, etc., and the effect is better than that of the direct Tea Polyphenol (TP) addition system, because the surface modification of tea polyphenol further improves the dispersion of the filler in the rubber matrix, and the interface combination of the filler and the rubber matrix is enhanced, the effect is better than that of the direct Tea Polyphenol (TP) addition system.
TABLE 1
TABLE 2
Example 2
Adding 50g of white carbon black (Silica) into 250ml of absolute ethyl alcohol, stirring for 3h at room temperature to fully dissolve the white carbon black in the absolute ethyl alcohol, adding 10g of Tea Polyphenol (TP) into the mixed solution, reacting for 7h at the reaction temperature of 60 ℃, washing the obtained reaction product with the absolute ethyl alcohol, centrifuging for several times, and drying to constant weight to obtain the final product.
The obtained biomass rubber antioxidant is named silical-s-TP. The synthesized product is shown to be a target product through infrared spectrum, ultraviolet absorbable spectrum and element analysis. The weight loss analysis of the silica-s-TP shows that the mass fraction of the tea polyphenol is 16.93 percent.
The basic formulation of a styrene-butadiene rubber composite prepared with the product Silica-s-TP is shown in Table 3 (unit: parts by weight phr).
TABLE 3
In order to better research the anti-aging performance of the rubber, the rubber is subjected to a thermal oxidation aging resistance performance test, and the thermal oxidation aging crosslinking density (shown in figure 3) shows that in a system added with a biomass rubber anti-aging agent silica-s-TP, the crosslinking density of an aged rubber composite material is increased most slowly, a lower crosslinking density value is still kept after 9 days of aging, and the effect is better than that of a system directly added with Tea Polyphenol (TP) and a system added with an anti-aging agent 4020; from the tensile retention curves of different days of thermo-oxidative aging (see FIG. 4), it is shown that the system with the addition of silica-s-TP has a higher tensile retention after 9 days of aging, while the tensile retention decreases most rapidly in the system with the direct addition of Tea Polyphenols (TP); and the tensile elongation retention rate curve (shown in figure 5) of the system after different days of thermo-oxidative aging shows that the thermo-oxidative aging resistant effect of the system added with the silica-s-TP is better than that of the system directly added with the Tea Polyphenol (TP) and the anti-aging agent 4020. Therefore, the silicon-s-TP has better anti-aging performance, and the anti-aging performance is higher than that of a system directly added with Tea Polyphenol (TP) and a system added with an anti-aging agent 4020.
Example 3
Adding 100g of nano microcrystalline cellulose (NCC) into 333ml of toluene solvent, stirring for 4h at room temperature, uniformly mixing, then adding 10g of Tea Polyphenol (TP) into the mixed solution, reacting for 10h at 80 ℃, washing the obtained product with the toluene solvent, centrifuging, and drying to constant weight to obtain the final product, thus obtaining the NCC-s-TP.
The infrared spectrum and the ultraviolet absorbable spectrum show that the synthesized final product is a target product through elemental analysis, and the thermal weight loss analysis shows that the mass fraction of the tea polyphenol in the biomass rubber antioxidant is 9.34 percent
The basic formulation of the natural rubber composite is shown in Table 4 (unit: parts by weight phr).
TABLE 4
The rubber composite material is subjected to a thermal-oxidative aging resistance test, and a crosslinking density curve (shown in figure 6) of thermal-oxidative aging shows that after 9 days of thermal-oxidative aging, the natural rubber composite material added with NCC-s-TP keeps a lower crosslinking density value, and the effect is better than that of a system directly added with Tea Polyphenol (TP) and a system added with an anti-aging agent 4020; as for the tensile retention rate curve (shown in figure 7) and the tensile elongation retention rate curve (shown in figure 8) of the rubber composite material, the direct addition of NCC-s-TP has better mechanical property retention rate, the effect is better than that of a system in which Tea Polyphenol (TP) and the anti-aging agent 4020 are added, and the anti-aging effect of NCC-s-TP is better than that of the anti-aging agent 4020 and the Tea Polyphenol (TP).
Example 4
Adding a 50g halloysite tube into 250ml petroleum ether solvent, stirring for 3h at room temperature to fully dissolve the nano filler in the petroleum ether, adding 10g Tea Polyphenol (TP) into the mixed solution, reacting for 7h at 65 ℃, washing the obtained reaction product with petroleum ether, centrifuging for several times, and drying to constant weight to obtain the final product.
The infrared spectrum and the ultraviolet absorbable spectrum show that the synthesized final product is a target product through elemental analysis, and the thermal weight loss analysis shows that the mass fraction of the tea polyphenol in the biomass rubber antioxidant is 12.39%.
Example 5
Adding 30g of montmorillonite into 300ml of ethyl acetate solvent, stirring at room temperature for 3.5h to fully dissolve the montmorillonite into the ethyl acetate, adding 30g of Tea Polyphenol (TP) into the mixed solution, reacting at the reaction temperature of 80 ℃ for 6h, washing the obtained product with ethyl acetate, centrifuging for several times, and drying to constant weight to obtain the final product.
The infrared spectrogram and the ultraviolet absorbable XPS and the element analysis show that the synthesized final product is a target product, and the thermal weight loss analysis shows that the mass fraction of the tea polyphenol in the biomass rubber antioxidant is 23.3%.
Claims (10)
1. A preparation method of a biomass rubber anti-aging agent is characterized in that biomass compound tea polyphenol is combined to the surface of an inorganic filler in a covalent bond mode through chemical reaction to obtain the biomass rubber anti-aging agent, and the preparation method comprises the following steps:
firstly, adding an inorganic filler into an organic solvent, and uniformly stirring and mixing to obtain a mixed solution;
secondly, adding biomass compound tea polyphenol into the mixed solution, and reacting at 40-80 ℃;
and thirdly, filtering, washing and drying a product obtained by the reaction to obtain the biomass rubber anti-aging agent.
2. The method of claim 1, wherein the inorganic filler is micro-or nano-sized inorganic particles.
3. The method according to claim 2, wherein the inorganic filler comprises one or more of white carbon black, halloysite, nanocrystalline cellulose, montmorillonite, mica powder, attapulgite, diatomaceous earth, kaolin, carbon black, talc, and silica powder.
4. The method according to claim 1, wherein the organic solvent is one of ethanol, toluene, ethyl acetate, and petroleum ether.
5. The preparation method according to claim 1, wherein the solid mass content of the inorganic filler in the mixed solution is 5% to 30%.
6. The method according to claim 1, wherein the stirring and mixing are carried out for 2 to 4 hours.
7. The method according to claim 1, wherein the inorganic filler is added in an amount of 1 to 10 times the mass of the tea polyphenol.
8. The method according to claim 1, wherein the reaction time is 4 to 10 hours.
9. A biomass rubber antioxidant produced by the production method according to any one of claims 1 to 8.
10. The biomass rubber antioxidant as claimed in claim 9, which is used for preparing natural rubber and synthetic rubber composite materials.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113930132A (en) * | 2021-11-17 | 2022-01-14 | 芜湖跃兆生物科技有限公司 | Gallic acid modified diatomite modified epoxy resin paint and preparation method thereof |
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