CN117735563A - Preparation method of modified white carbon black for rubber reinforcement - Google Patents

Preparation method of modified white carbon black for rubber reinforcement Download PDF

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Publication number
CN117735563A
CN117735563A CN202311799097.2A CN202311799097A CN117735563A CN 117735563 A CN117735563 A CN 117735563A CN 202311799097 A CN202311799097 A CN 202311799097A CN 117735563 A CN117735563 A CN 117735563A
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carbon black
white carbon
modified white
rubber reinforcement
silicon oxide
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CN202311799097.2A
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张莉娜
方春平
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Jiangsu Ate Polymer Materials Co ltd
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Jiangsu Ate Polymer Materials Co ltd
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Abstract

The invention discloses a preparation method of modified white carbon black for a rubber reinforcing agent, which comprises the following specific steps: s1: soaking rice hulls in dilute hydrochloric acid for 18-24h, cleaning the rice hulls to pH 7, and drying to obtain pretreated rice hulls; s2: the pretreated rice hulls are put into a combustion furnace to be combusted for 4 to 5 hours, and rice hull ash is obtained; s3: mixing rice hull ash in an active water solution, and adding sodium hydroxide to react to obtain a sodium metasilicate water solution; s4: controlling the pH value of the sodium metasilicate aqueous solution to be 8-9, then adding sulfuric acid with a certain concentration to carry out precipitation reaction under a certain reaction condition, and cleaning, acidifying, aging, filtering, drying and crushing reactants to obtain amorphous nano silicon oxide; s5, uniformly mixing amorphous nano silicon oxide and a surface auxiliary agent in a certain proportion to obtain a final product. The invention adopts rice husk as raw material and adopts improved chemical precipitation method to prepare amorphous silicon oxide, and the amorphous silicon oxide is premixed with surface auxiliary agent, so as to improve the reinforcing performance of white carbon black on rubber.

Description

Preparation method of modified white carbon black for rubber reinforcement
Technical Field
The invention belongs to the field of rubber additives, and particularly relates to a preparation method of modified white carbon black for a rubber reinforcing agent.
Background
Raw rubber, also known as rubber, is an important natural product. It has wide application field, from automobile tyre to medical articles, it is not separated from its existence. Generally, raw rubber is a linear macromolecular chain, the mechanical properties are poor, and a reinforcing agent is generally required to be used for obtaining rubber products meeting various service properties. The interaction between the reinforcing agent and the rubber has an important relationship to the reinforcing properties of the rubber. Many properties of rubber, such as abrasion resistance, elasticity, strength and dynamic properties, are related to the reinforcing effect of the most rubber of the reinforcing agent. These properties are of great importance for the service life of rubber products, in particular tires.
White carbon black is one of the most important reinforcing agents for rubber. The vulcanized rubber reinforced by the white carbon black has the characteristics of higher tearing strength, low dynamic heat generation of the vulcanized rubber, good dynamic fatigue performance, capability of improving the adhesive strength of rubber, metal and cords, and the like. However, the surface polarity and hydrophilicity of the white carbon black are strong, so that the compatibility of the white carbon black with hydrocarbon rubber molecules is poor, and if the white carbon black is filled in a large amount in rubber, the reinforcing effect such as tensile strength, abrasion resistance and the like of the white carbon black are reduced.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a preparation method of modified white carbon black for rubber reinforcing agent, which adopts rice husk as a raw material to prepare amorphous silicon oxide by adopting an improved chemical precipitation method, and pre-mixes the amorphous silicon oxide with a surface auxiliary agent, thereby improving the reinforcing performance of the white carbon black on rubber.
The technical scheme adopted in the invention is as follows:
the preparation method of the modified white carbon black for rubber reinforcement comprises the following specific steps:
s1: soaking rice hulls in dilute hydrochloric acid for 18-24h, cleaning the rice hulls to pH 7, and drying to obtain pretreated rice hulls;
s2: the pretreated rice hulls are put into a combustion furnace to be combusted for 4 to 5 hours, and rice hull ash is obtained;
s3: mixing rice hull ash in an active water solution, and adding sodium hydroxide into the active water solution to react to obtain a sodium metasilicate water solution with a certain concentration;
s4: controlling the pH value of the sodium metasilicate aqueous solution to be 8-9, then adding sulfuric acid with a certain concentration to carry out precipitation reaction under a certain reaction condition, and cleaning, acidifying, aging, filtering, drying and crushing reactants to obtain amorphous nano silicon oxide;
s5, uniformly mixing amorphous nano silicon oxide and a surface auxiliary agent in a certain proportion to obtain a final product.
Preferably, in the S1, the concentration of the dilute hydrochloric acid is 0.7-1.2mol/L.
Preferably, in S2, the combustion temperature is controlled to 650-700 ℃.
Preferably, in S3, the active aqueous solution is an anionic active agent aqueous solution.
Preferably, in the step S3, the anionic active agent is one or two of sodium hexadecyl sulfonate, sodium dodecyl benzene sulfonate and sodium polyacrylate, and the amount of the anionic active agent is 3% -8% of the mass of the rice hull ash.
Preferably, in the step S3, the concentration of the sodium metasilicate solution is 0.25-0.45mol/L.
Preferably, in the S4, the concentration of sulfuric acid is 0.35-0.55mol/L.
Preferably, in the step S4, the precipitation reaction time is 40-60min, and the reaction temperature is 55-65 ℃.
Preferably, in the step S5, the addition amount of the surface auxiliary agent is 5% -10% of the mass of the amorphous nano silicon oxide.
Preferably, in S5, the surface auxiliary agent is one or a mixture of more of amine or alcohol surface auxiliary agents.
The beneficial effects are that: the invention provides a preparation method of modified white carbon black for a rubber reinforcing agent, which has the following advantages compared with the prior art:
(1) The invention adopts rice husk as raw material and adopts improved chemical precipitation method to prepare amorphous silicon oxide, because the surface of white carbon black extracted from rice husk ash has residual organic matter component, compared with conventional hundred carbon black, the invention can effectively improve the compatibility with rubber, and the amorphous silicon oxide is uniformly dispersed in rubber system in nano-scale size, has good reinforcing effect and has good economic value and social significance.
(2) In the invention, the anionic active agent is used for treating the rice hull ash solution in the preparation process of amorphous silicon oxide, so that impurities attached to the rice hull ash framework can be further removed, and the whiteness and the silicon oxide content of the product are improved.
(3) In the invention, in order to avoid delayed vulcanization caused by the adsorption of the accelerator and the antioxidant added in the rubber mixing process of the white carbon black, amine and alcohol surface auxiliary agents are premixed in the white carbon black, and the substances are preferentially adsorbed on the surface of the white carbon black, so that the adsorption of the white carbon black to the accelerator is weakened.
Description of the embodiments
In order to better understand the technical solutions in the present application, the following description will clearly and completely describe the technical solutions in the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, shall fall within the scope of the present application.
Examples
The preparation method of the modified white carbon black for the rubber reinforcing agent comprises the following specific steps:
s1: soaking rice hulls in dilute hydrochloric acid (1.2 mol/L) for 24 hours, cleaning the rice hulls to pH 7, and drying to obtain pretreated rice hulls;
s2: the pretreated rice hulls are put into a combustion furnace to be combusted for 4.5 hours at 650 ℃ to obtain rice hull ash;
s3: mixing rice hull ash in an active water solution (the mass ratio of sodium hexadecyl sulfonate to sodium polyacrylate is 1:1), and adding sodium hydroxide into the active water solution to react to obtain a sodium metasilicate water solution with the concentration of 0.25 mol/L;
s4: controlling the pH value of the sodium metasilicate aqueous solution to be 8, then adding 0.4mol/L sulfuric acid to carry out precipitation reaction at 60 ℃ for 60min, and washing, acidifying, aging, filtering, drying and crushing reactants to obtain amorphous nano silicon oxide;
s5, uniformly mixing amorphous nano silicon oxide and a surface auxiliary agent (polyethylene glycol-4000) in a certain proportion to obtain a final product, wherein the addition amount of the surface auxiliary agent is 5% of the mass of the amorphous nano silicon oxide.
Examples
The preparation method of the modified white carbon black for the rubber reinforcing agent comprises the following specific steps:
s1: soaking rice hulls in dilute hydrochloric acid (1.2 mol/L) for 24 hours, cleaning the rice hulls to pH 7, and drying to obtain pretreated rice hulls;
s2: the pretreated rice hulls are put into a combustion furnace to be combusted for 4.5 hours at 650 ℃ to obtain rice hull ash;
s3: mixing rice hull ash in an active water solution (the mass ratio of sodium hexadecyl sulfonate to sodium polyacrylate is 1:1), and adding sodium hydroxide into the active water solution to react to obtain a sodium metasilicate water solution with the concentration of 0.3 mol/L;
s4: controlling the pH value of the sodium metasilicate aqueous solution to be 8, then adding 0.5mol/L sulfuric acid to carry out precipitation reaction at 60 ℃ for 60min, and washing, acidifying, aging, filtering, drying and crushing reactants to obtain amorphous nano silicon oxide;
s5, uniformly mixing amorphous nano silicon oxide and a surface auxiliary agent (polyethylene glycol-4000) in a certain proportion to obtain a final product, wherein the addition amount of the surface auxiliary agent is 8% of the mass of the amorphous nano silicon oxide.
Examples
The preparation method of the modified white carbon black for the rubber reinforcing agent comprises the following specific steps:
s1: soaking rice hulls in dilute hydrochloric acid (1.2 mol/L) for 24 hours, cleaning the rice hulls to pH 7, and drying to obtain pretreated rice hulls;
s2: the pretreated rice hulls are put into a combustion furnace to be combusted for 4.5 hours at 650 ℃ to obtain rice hull ash;
s3: mixing rice hull ash in an active water solution (the mass ratio of sodium dodecyl benzene sulfonate to sodium polyacrylate is 1:1), and adding sodium hydroxide into the active water solution to react to obtain a sodium metasilicate water solution with the concentration of 0.3 mol/L;
s4: controlling the pH value of the sodium metasilicate aqueous solution to be 8, then adding 0.5mol/L sulfuric acid to carry out precipitation reaction at 60 ℃ for 60min, and washing, acidifying, aging, filtering, drying and crushing reactants to obtain amorphous nano silicon oxide;
s5, uniformly mixing amorphous nano silicon oxide and a surface auxiliary agent (polyethylene glycol-4000) in a certain proportion to obtain a final product, wherein the addition amount of the surface auxiliary agent is 10% of the mass of the amorphous nano silicon oxide.
Test formula (in parts by mass): NR (Nanjing excellent Baolong rubber and plastic Co., ltd.) 100; carbon black N330 20; zinc oxide 4; stearin 2; silane coupling agent KH-550; coumarone 3; anti-aging agent 4010 2; sulfur 2.5, vulcanization accelerator TBBS 1.5; accelerator TMTD 0.2, white carbon 20.
The white carbon blacks prepared in example 1, example 2 and example 3 and the common white carbon black (A-200, dewar chemical industry) of comparative example are respectively applied to the test formulas, and are mixed by adopting a three-stage mixing process, so as to obtain the mixed sizing material. The reinforcing performance of the mixed rubber materials is respectively tested and compared according to the national standard, and the test results are shown in table 1.
Table 1 shows the reinforcing property test results of each sample
As can be seen from Table 1, the rubber compounds of examples 1 to 3 have improved tensile stress, tensile strength and tear strength, and have better reinforcing properties, and abrasion resistance and hardness substantially maintain the same level as those of the comparative examples. This is because the amorphous silica prepared by the improved chemical precipitation method and the white carbon black extracted from rice hull ash in examples 1 to 3 has organic components remaining on the surface, the compatibility with rubber can be effectively improved as compared with the comparative example, and the reinforcing effect is good because the amorphous silica is uniformly dispersed in the rubber system in a nano-scale size.
The compounds of examples 1-3 have reduced mooney scorch time, increased mooney viscosity and reduced cure rate compared to the comparative examples. The white carbon black particles have higher specific surface energy, and can adsorb a plurality of small organic molecular substances, such as an accelerator, an anti-aging agent and other related auxiliary agents added in the rubber mixing process, so that the content of the related vulcanization auxiliary agents is reduced, delayed vulcanization is generated, and the vulcanization effect is influenced. Therefore, in order to generate the delayed vulcanization phenomenon, in examples 1-3, amine or alcohol surface additives (such as polyethylene glycol-4000) are premixed in the amorphous white carbon black, so that the amine or alcohol surface additives can be preferentially adsorbed on the surface of the white carbon black during mixing, and the adsorption of the white carbon black to the vulcanization additives is weakened, so that the vulcanization performance of the sizing material is improved.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (10)

1. The preparation method of the modified white carbon black for rubber reinforcement is characterized by comprising the following specific steps:
s1: soaking rice hulls in dilute hydrochloric acid for 18-24h, cleaning the rice hulls to pH 7, and drying to obtain pretreated rice hulls;
s2: the pretreated rice hulls are put into a combustion furnace to be combusted for 4 to 5 hours, and rice hull ash is obtained;
s3: mixing rice hull ash in an active water solution, and adding sodium hydroxide into the active water solution to react to obtain a sodium metasilicate water solution with a certain concentration;
s4: controlling the pH value of the sodium metasilicate aqueous solution to be 8-9, then adding sulfuric acid with a certain concentration to carry out precipitation reaction under a certain reaction condition, and cleaning, acidifying, aging, filtering, drying and crushing reactants to obtain amorphous nano silicon oxide;
s5, uniformly mixing amorphous nano silicon oxide and a surface auxiliary agent in a certain proportion to obtain a final product.
2. The method for producing a modified white carbon black for rubber reinforcement according to claim 1, wherein in S1, the concentration of the dilute hydrochloric acid is 0.7 to 1.2mol/L.
3. The method for producing a modified white carbon black for rubber reinforcement according to claim 1, wherein in S2, the combustion temperature is controlled to 650 to 700 ℃.
4. The method for producing a modified white carbon black for rubber reinforcement according to claim 1, wherein in S3, the active aqueous solution is an anionic active agent aqueous solution.
5. The method for preparing modified white carbon black for rubber reinforcement according to claim 4, wherein in S3, the anionic active agent is one or two of sodium hexadecyl sulfonate, sodium dodecyl benzene sulfonate and sodium polyacrylate, and the amount of the anionic active agent is 3-8% of the mass of rice hull ash.
6. The method for producing a modified white carbon black for rubber reinforcement according to claim 1, wherein in S3, the concentration of the sodium metasilicate solution is 0.25 to 0.45mol/L.
7. The method for producing a modified white carbon black for rubber reinforcement according to claim 1, wherein the concentration of sulfuric acid in S4 is 0.35 to 0.55mol/L.
8. The method for preparing modified white carbon black for rubber reinforcement according to claim 1, wherein in S4, the precipitation reaction time is 40-60min and the reaction temperature is 55-65 ℃.
9. The method for preparing modified white carbon black for rubber reinforcement according to claim 1, wherein in the step S5, the addition amount of the surface auxiliary agent is 5% -10% of the mass of the amorphous nano silicon oxide.
10. The method for preparing modified white carbon black for rubber reinforcement according to claim 1, wherein in S5, the surface auxiliary agent is one or a mixture of more of amine or alcohol surface auxiliary agents.
CN202311799097.2A 2023-12-26 2023-12-26 Preparation method of modified white carbon black for rubber reinforcement Pending CN117735563A (en)

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CN202311799097.2A CN117735563A (en) 2023-12-26 2023-12-26 Preparation method of modified white carbon black for rubber reinforcement

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311799097.2A CN117735563A (en) 2023-12-26 2023-12-26 Preparation method of modified white carbon black for rubber reinforcement

Publications (1)

Publication Number Publication Date
CN117735563A true CN117735563A (en) 2024-03-22

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