A carbon black modifier and a method for modifying carbon black using the carbon black modifier

Abstract

The present invention discloses a carbon black modifier and a method for modifying carbon black by using the carbon black modifier, which relates to the technical field of carbon black production. After carboxymethyl chitosan, polyamide-amine and bis-sulfonylimide salt ionic liquid are compounded, they are subjected to microfluidics and ultrasonic treatment with carbon black, and finally the obtained modified carbon black is pre-cured and cross-linked to finally obtain highly dispersed carbon black. The modification cost is low, and the dispersion effect of carbon black is greatly improved.

Description

Technical Field

[0001] The invention relates to the technical field of carbon black production, and in particular to a carbon black modifier and a method for modifying carbon black using the carbon black modifier. Background Art

[0002] Carbon black is a black powdery substance formed by incomplete combustion or pyrolysis of hydrocarbons in the gas phase under strictly controlled process conditions. It is mainly composed of carbon and contains small amounts of elements such as oxygen, hydrogen and sulfur. The surface of carbon black particles lacks polar groups, which makes their surface inert, thus affecting their dispersibility and compatibility in the substrate. Specifically, when carbon black is added to the substrate as a reinforcing material, it will face problems such as poor compatibility with the substrate and poor particle dispersion. These shortcomings have largely restricted the scope of application of carbon black.

[0003] When modifying carbon black by mechanical dispersion method, high energy consumption, large equipment wear and tear will occur, and the long-term use cost is high. Excessive shearing may destroy the original structure of carbon black and affect its reinforcement performance. When adding dispersant for modification, excessive dispersant may occur, resulting in reduced mechanical properties such as tensile strength and aging resistance of the product, or causing defects such as precipitation and reduced gloss on the surface of the product. Summary of the invention

[0004] The first technical problem to be solved by the present invention is: in view of the deficiencies in the prior art, a carbon black modifier is provided, which has low cost and improves the dispersion effect of carbon black after use.

[0005] To solve the above-mentioned first technical problem, the technical solution of the present invention is:

[0006] A carbon black modifier comprises a compound of bissulfonyl imide salt ionic liquid, polyamide-amine and carboxymethyl chitosan, wherein the mass ratio of the carboxymethyl chitosan to the bissulfonyl imide salt ionic liquid and the polyamide-amine is 1:0.2 to 1:0.5 to 2.

[0007] The second technical problem to be solved by the present invention is: to address the deficiencies in the prior art and to provide a carbon black modification method which has low cost and improves the dispersion effect of carbon black.

[0008] To solve the above second technical problem, the technical solution of the present invention is:

[0009] A carbon black modification method, the preparation steps are:

[0010] S01, dissolving carboxymethyl chitosan in deionized water, and stirring until the carboxymethyl chitosan is completely dissolved;

[0011] S02, continue to add polyamide-amine and stir to make the polyamide-amine and carboxymethyl chitosan solution fully mixed;

[0012] S03. Add a bisulfonimide salt ionic liquid, continue stirring, and then perform ultrasonic treatment to obtain a compound solution;

[0013] S04. Add carbon black to the microfluidic system and mix the carbon black with the compound solution under a pressure of 0.7 - 0.9 MPa to obtain a mixed solution;

[0014] S05. Subject the mixed solution to ultrasonic treatment and then perform spray drying to obtain modified carbon black;

[0015] S06. Pre - cure and cross - link the modified carbon black to finally obtain highly dispersed carbon black.

[0016] Preferably, in step S01, the mass ratio of carboxymethyl chitosan to deionized water is 1:50 - 100, the stirring speed is 150 - 300 r / min, and the stirring time is 30 - 60 min.

[0017] Preferably, in step S02, the stirring speed is 180 - 400 r / min, and the stirring time is 15 - 30 min.

[0018] Preferably, in step S03, the stirring speed is 200 - 500 r / min, the ultrasonic power is 100 - 300 W, and the ultrasonic time is 30 - 50 min.

[0019] Preferably, in step S04, the mass ratio of carbon black to the compound solution is 1:1 - 1:3.

[0020] Preferably, in step S04, the aspect ratio of the microfluidic channel is 10:1 - 15:1, and the flow rate of the microfluidic system is controlled at 1 - 3 mL / min.

[0021] Preferably, in step S05, the inlet air temperature of the spray drying is controlled at 150 - 200 °C, and the outlet air temperature is controlled at 80 - 120 °C.

[0022] Preferably, in step S05, the ultrasonic frequency is 20 kHz / 100 W, and the ultrasonic time is 5 - 10 s.

[0023] Preferably, in step S06, the pre - curing temperature is 80 - 82 °C, the pre - curing time is 10 - 20 min, the cross - linking temperature is 120 - 125 °C, and the cross - linking time is 15 - 30 min.

[0024] Due to the adoption of the above - mentioned technical solution, the beneficial effects of the present invention are:

[0025] 1. The carboxyl groups of carboxymethyl chitosan and the amino groups of polyamide-amine form polyelectrolyte complexes through electrostatic interactions to construct a multi-layer adsorption layer on the surface of carbon black. Carboxymethyl chitosan forms hydrogen bonds with the hydroxyl groups on the surface of carbon black through carboxyl groups to provide initial anchoring. The dendritic structure of polyamide-amine prevents the aggregation of carbon black through steric hindrance effects. At the same time, its amino groups can further electrostatically bind to the anions of bis-sulfonimide salt ionic liquids to enhance stability. After the bis-sulfonimide salt is adsorbed on the surface of carbon black, the electrostatic repulsion between carbon blacks is enhanced through the negative charges of the anions, forming a "double insurance" with the steric hindrance of carboxymethyl chitosan / polyamide-amine, achieving double stability of electrostatics-steric hindrance.

[0026] 2. The low surface tension of bis-sulfonimide salt ionic liquids can rapidly penetrate the microporous structure of carbon black, while the amphiphilicity of carboxymethyl chitosan (hydrophilic carboxyl + hydrophobic backbone) can reduce the interfacial tension between carbon black and polar matrices (such as rubber), promoting wetting. The terminal amino groups of polyamide-amine can form hydrogen bonds with the cations of bis-sulfonimide salt ionic liquids and the carboxyl groups of carboxymethyl chitosan, enhancing the co-adsorption of the three on the surface of carbon black to form a uniform coating layer.

[0027] 3. Bis-sulfonimide salt ionic liquids can act as "molecular lubricants" at high temperatures, reducing the glass transition temperature (Tg) of the carboxymethyl chitosan / polyamide-amine network, enabling the modified layer to remain flexible during processing and avoiding the detachment of dispersants caused by stress concentration.

[0028] 4. Pre-curing enables carboxymethyl chitosan / polyamide-amine to be initially bound through hydrogen bonds. During high-temperature cross-linking, the sulfonylimide groups in bis-sulfonimide salt ionic liquids can undergo condensation reactions with the hydroxyl groups of carboxymethyl chitosan and the amino groups of polyamide-amine to form a covalent bond network, significantly improving the binding strength between the dispersant and carbon black.

[0029] 5. High-intensity shear forces are generated in the microfluidic channel to break the primary aggregates of carbon black, forming nano-scale dispersion. Compared with traditional mechanical dispersion, it has lower energy consumption and avoids excessive shear damage to the carbon black structure, ensuring sufficient contact between carbon black and the compounding liquid in the microchannel and avoiding secondary aggregation caused by local concentration unevenness.

[0030] 6. Through the triple action mechanism of interface engineering - microfluidics - ultrasound cooperation, efficient dispersion of carbon black in non-polar systems is achieved, breaking through the balance problem between dispersibility and functionality in traditional methods, and significantly improving the dispersion uniformity in the rubber matrix. Detailed implementation manners

[0031] The present invention will be further elaborated below in conjunction with embodiments. Example 1

[0032] A method for modifying carbon black, and its preparation steps are as follows:

[0033] S01: The mass ratio of carboxymethyl chitosan to deionized water is 1:50, the stirring speed is 150 r / min, and the stirring time is 30 min.

[0034] S02: After adding polyamidoamine, the stirring speed is 180 r / min and the stirring time is 15 min.

[0035] S03: The addition amount of disulfonimide salt ionic liquid is 0.2 times the mass of carboxymethyl chitosan, and that of polyamidoamine is 0.5 times the mass; the stirring speed is 200 r / min, the ultrasonic power is 100 W, and the ultrasonic time is 30 min.

[0036] S04: The mass ratio of carbon black (N330) to the compound solution is 1:1, the microfluidic pressure is 0.7 MPa, the channel width-to-height ratio is 10:1, and the flow rate is 1 mL / min.

[0037] S05: Ultrasonic treatment for 5 s, the inlet air temperature of spray drying is 150 °C, and the outlet air temperature is 80 °C.

[0038] S06: The pre-curing temperature is 80 °C and the time is 10 min; the cross-linking temperature is 120 °C and the time is 15 min to obtain highly dispersed carbon black. Example 2

[0039] A method for modifying carbon black, and its preparation steps are as follows:

[0040] S01: The mass ratio of carboxymethyl chitosan to deionized water is 1:100, the stirring speed is 300 r / min, and the stirring time is 60 min.

[0041] S02: After adding polyamidoamine, the stirring speed is 400 r / min and the stirring time is 30 min.

[0042] S03: The addition amount of disulfonimide salt ionic liquid is 1 times the mass of carboxymethyl chitosan, and that of polyamidoamine is 2 times the mass; the stirring speed is 500 r / min, the ultrasonic power is 300 W, and the ultrasonic time is 50 min.

[0043] S04: The mass ratio of carbon black (N330) to the compound solution is 1:3, the microfluidic pressure is 0.9 MPa, the channel width-to-height ratio is 15:1, and the flow rate is 3 mL / min.

[0044] S05: Ultrasonic treatment for 10 s, the inlet air temperature of spray drying is 200 °C, and the outlet air temperature is 120 °C.

[0045] S06: The pre-curing temperature is 82 °C and the time is 20 min; the cross-linking temperature is 125 °C and the time is 30 min to obtain highly dispersed carbon black. Example 3

[0046] A method for modifying carbon black, and its preparation steps are as follows:

[0047] S01: The mass ratio of carboxymethyl chitosan to deionized water is 1:75, the stirring speed is 200 r / min, and the stirring time is 45 min.

[0048] S02: After adding polyamidoamine, the stirring speed is 250 r / min and the stirring time is 20 min.

[0049] S03: The addition amount of disulfonimide salt ionic liquid is 0.5 times the mass of carboxymethyl chitosan, and that of polyamidoamine is 1 times the mass; the stirring speed is 300 r / min, the ultrasonic power is 200 W, and the ultrasonic time is 40 min.

[0050] S04: The mass ratio of carbon black (N660) to the compound solution is 1:2, the microfluidic pressure is 0.8 MPa, the channel width-to-height ratio is 12:1, and the flow rate is 2 mL / min.

[0051] S05: The ultrasonic treatment time is 8 s, the inlet air temperature for spray drying is 175 °C, and the outlet air temperature is 100 °C.

[0052] S06: The pre-curing temperature is 81 °C and the time is 15 min; the cross-linking temperature is 122 °C and the time is 20 min to obtain highly dispersed carbon black. Example 4

[0053] A method for modifying carbon black, and its preparation steps are as follows:

[0054] S01: The mass ratio of carboxymethyl chitosan to deionized water is 1:80, the stirring speed is 250 r / min, and the stirring time is 50 min.

[0055] S02: After adding polyamidoamine, the stirring speed is 300 r / min and the stirring time is 25 min.

[0056] S03: The addition amount of disulfonimide salt ionic liquid is 0.8 times the mass of carboxymethyl chitosan, and that of polyamidoamine is 1.5 times the mass; the stirring speed is 400 r / min, the ultrasonic power is 250 W, and the ultrasonic time is 45 min.

[0057] S04: The mass ratio of carbon black (N660) to the compound solution is 1:2.5, the microfluidic pressure is 0.85 MPa, the channel width-to-height ratio is 13:1, and the flow rate is 2.5 mL / min.

[0058] S05: The ultrasonic treatment time is 7 s, the inlet air temperature for spray drying is 180 °C, and the outlet air temperature is 90 °C.

[0059] S06: The pre-curing temperature is 80 °C and the time is 18 min; the cross-linking temperature is 123 °C and the time is 25 min to obtain highly dispersed carbon black. Comparative Example 1

[0060] Only carboxymethyl chitosan was added, and polyamidoamine and disulfonimide salt ionic liquid were not added. The remaining control parameters were the same as those in Example 2, and the obtained product was dispersed carbon black. Comparative Example 2

[0061] Only polyamidoamine was added, and carboxymethyl chitosan and disulfonimide salt ionic liquid were not added. The remaining control parameters were the same as those in Example 2, and the obtained product was dispersed carbon black. Comparative Example 3

[0062] Only disulfonimide salt ionic liquid was added, and carboxymethyl chitosan and polyamidoamine were not added. The remaining control parameters were the same as those in Example 2, and the obtained product was dispersed carbon black.

[0063] The highly dispersed carbon black in Examples 1-4, the dispersed carbon black in Comparative Examples 1-3, and carbon black N330 were taken as blank experiments for performance testing. The experimental results are as follows:

[0064] Table 1

[0065]

[0066] It can be seen from the data in the table that polyamidoamine, disulfonimide salt ionic liquid and carboxymethyl chitosan significantly reduce the agglomeration of carbon black, enhance the binding force at the matrix interface, and the cross-linked structure formed with carbon black enhances the resistance to chemical erosion. The three-dimensional network delays thermal decomposition, increases active sites, and improves the adsorption effect.

[0067] It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

Claims

1. A method for modifying carbon black using a carbon black modifier, characterized in that: The carbon black modifier comprises a compound of a bissulfonyl imide salt ionic liquid, polyamide-amine and carboxymethyl chitosan, wherein the mass ratio of the carboxymethyl chitosan to the bissulfonyl imide salt ionic liquid and the polyamide-amine is 1:0.2 to 1:0.5 to 2; When the carbon black modifier modifies carbon black, the method comprises the following steps: S01, dissolving carboxymethyl chitosan in deionized water, and stirring until the carboxymethyl chitosan is completely dissolved; S02, continue to add polyamide-amine and stir to make the polyamide-amine and carboxymethyl chitosan solution fully mixed; S03, adding bissulfonyl imide salt ionic liquid, continuing stirring, and then ultrasonicating to obtain a composite solution; S04, adding carbon black into the microfluidic system, and mixing the carbon black and the compound liquid under a pressure of 0.7-0.9 MPa to obtain a mixed liquid; S05, the mixed solution is subjected to ultrasonic treatment and then spray-dried to obtain modified carbon black; S06. The modified carbon black is pre-cured and cross-linked to finally obtain highly dispersed carbon black.

2. A method for modifying carbon black using a carbon black modifier as claimed in claim 1, characterized in that: In step S01, the mass ratio of carboxymethyl chitosan to deionized water is 1:50-100, the stirring speed is 150-300 r / min, and the stirring time is 30-60 min.

3. A method for modifying carbon black using a carbon black modifier as claimed in claim 1, characterized in that: In step S02, the stirring speed is 180-400 r / min, and the stirring time is 15-30 min.

4. The method for modifying carbon black using a carbon black modifier according to claim 1, characterized in that: In step S03, the stirring speed is 200-500 r / min, the ultrasonic power is 100-300 W, and the ultrasonic time is 30-50 min.

5. The method for modifying carbon black using a carbon black modifier according to claim 1, characterized in that: In step S04, the mass ratio of carbon black to compound liquid is 1:1 to 1:

3.

6. A method for modifying carbon black using a carbon black modifier as claimed in claim 1, characterized in that: In step S04, the aspect ratio of the microfluidic channel is 10:1 to 15:1, and the flow rate of the microfluidic system is controlled at 1 to 3 mL / min.

7. The method for modifying carbon black using a carbon black modifier according to claim 1, characterized in that: In step S05, the inlet air temperature of the spray drying is controlled at 150-200°C, and the outlet air temperature is controlled at 80-120°C.

8. The method for modifying carbon black using a carbon black modifier according to claim 1, characterized in that: In step S05, the ultrasonic frequency is 20kHz / 100W, and the ultrasonic time is 5 to 10s.

9. The method for modifying carbon black using a carbon black modifier according to claim 1, characterized in that: In step S06, the pre-curing temperature is 80-82° C., the pre-curing time is 10-20 min, the cross-linking temperature is 120-125° C., and the cross-linking time is 15-30 min.

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