A preparation method of modified carbon black and its application

Abstract

The present disclosure relates to a method for preparing modified carbon black, which comprises the following steps: step 1: dissolving dodecenyl succinic anhydride and nadic anhydride in an organic solvent to obtain a first solution; step 2: adding carbon black to the first solution, stirring at room temperature for 1-3 hours, and then ultrasonicating for 5-60 minutes to obtain a solution containing a mixture; step 3: separating the solid and the solvent in the solution containing the mixture, and keeping the solid at 120°C-200°C for 3-8 hours to obtain modified carbon black. The modified carbon black obtained by the present disclosure has both high blackness and good stability.

Description

Technical Field

[0001] The present disclosure relates to the technical field of carbon black materials, and in particular to a preparation method of modified carbon black and applications thereof. Background Art

[0002] Carbon black refers to a black powdery substance formed by incomplete combustion or pyrolysis of hydrocarbons under harsh conditions. It is the most frequently used raw material in modern industry. As the oldest industrial raw material, carbon black is widely used in tires, rubber, plastics, paints, printing and other fields. Among them, carbon black is most widely used in the tire field, accounting for 66.7% of the application field of carbon black. However, carbon black particles have very few polar groups on their surface, which makes their surface inert. Therefore, when added to the substrate as a reinforcing material, there will be disadvantages such as poor compatibility with the substrate and poor particle dispersion, which seriously limits the application of carbon black particles. Therefore, it is very necessary to perform surface modification on carbon black when it is used.

[0003] As a kind of amorphous carbon, carbon black has a structure similar to disordered graphite and is formed by incomplete combustion of aromatic hydrocarbons at high temperatures. Aromatic hydrocarbon molecules dissociate by breaking carbon-hydrogen bonds at high temperatures, and carbon atoms and aromatic free radicals can react to form layered hexagonal carbon ring structures. These carbon rings tend to stack into 3-4 layers of crystal structures, and the edges of the layers are mainly composed of hydrogen, free radicals and oxygen-containing functional groups. The oxygen-containing functional groups on the surface of the carbon ring structure are low in content and have good chemical reactivity, which provides possibilities for surface modification of carbon black. Summary of the invention

[0004] The present invention provides a preparation method of modified carbon black and its application to solve the deficiencies in the related art.

[0005] According to a first aspect of an embodiment of the present disclosure, there is provided a method for preparing modified carbon black, comprising:

[0006] Step 1: dissolving dodecenylsuccinic anhydride and / or nadic anhydride in an organic solvent to obtain a first solution;

[0007] Step 2: adding carbon black to the first solution, stirring at room temperature for 1-3 hours, and then ultrasonicating for 5-60 minutes to obtain a solution containing a mixture;

[0008] Step 3: Separating the solid and the solvent in the solution containing the mixture, and keeping the solid at 120° C.-200° C. for 3-8 hours to obtain the modified carbon black.

[0009] In one aspect of the present disclosure, the mass ratio of the dodecenylsuccinic anhydride to the nadic anhydride is selected from (0.5-3):1.

[0010] In one aspect of the present disclosure, the mass ratio of the dodecenylsuccinic anhydride to the nadic anhydride is selected from (1.2-2):1; preferably, the mass ratio of the dodecenylsuccinic anhydride to the nadic anhydride is selected from (1.2-1.6):1; specifically, the mass ratio of the dodecenylsuccinic anhydride to the nadic anhydride is selected from 1.5:1.

[0011] In one aspect of the present disclosure, the ratio of the sum of the masses of the dodecenylsuccinic anhydride and the nadic anhydride to the mass of the carbon black is selected from (0.05-0.3):1.

[0012] In one aspect of the present disclosure, the ratio of the sum of the masses of the dodecenylsuccinic anhydride and the nadic anhydride to the mass of the carbon black is selected from (0.05-0.12):1.

[0013] In one aspect of the present disclosure, the organic solvent is selected from acetone.

[0014] In one aspect of the present disclosure, the ultrasonic process is: ultrasonic at 20-80 kHz for 5-60 minutes; preferably, ultrasonic at 20-60 kHz for 25-45 minutes; specifically, ultrasonic at 40 kHz for 30 minutes.

[0015] In one aspect of the present disclosure, there is provided a method for preparing modified carbon black, comprising:

[0016] Step 1: dissolving dodecenylsuccinic anhydride and nadic anhydride in acetone to obtain a first solution; the ratio of the sum of the masses of dodecenylsuccinic anhydride and the nadic anhydride to the mass of the carbon black is selected from (0.05-0.3):1, preferably (0.05-0.12):1.

[0017] Step 2: adding carbon black to the first solution, stirring at room temperature for 1-3 hours, and then ultrasonicating at 20-60 kHz for 25-45 minutes to obtain a solution containing a mixture;

[0018] Step 3: Separating the solid and the solvent in the solution containing the mixture, and keeping the solid at 160° C.-200° C. for 3-8 hours to obtain the modified carbon black.

[0019] According to a second aspect of an embodiment of the present disclosure, a modified carbon black is provided, wherein the modified carbon black is prepared by the aforementioned preparation method.

[0020] The technical solution provided by the embodiments of the present disclosure may have the following beneficial effects:

[0021] It can be seen from the above embodiments that the present disclosure obtains a modified carbon black having both high blackness and good stability by modifying the surface of carbon black.

[0022] It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the present disclosure. DETAILED DESCRIPTION

[0023] The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present disclosure. Instead, they are merely examples of devices and methods consistent with some aspects of the present disclosure as detailed in the appended claims.

[0024] The terms used in this disclosure are for the purpose of describing specific embodiments only and are not intended to limit the disclosure. The singular forms of "a", "said" and "the" used in this disclosure and the appended claims are also intended to include plural forms unless the context clearly indicates otherwise. It should also be understood that the term "and / or" used herein refers to and includes any or all possible combinations of one or more associated listed items.

[0025] It should be understood that although the terms first, second, third, etc. may be used in the present disclosure to describe various information, such information should not be limited to these terms. These terms are only used to distinguish the same type of information from each other. For example, without departing from the scope of the present disclosure, the first information may also be referred to as the second information, and similarly, the second information may also be referred to as the first information. Depending on the context, the word "if" as used herein may be interpreted as "at the time of" or "when" or "in response to determining".

[0026] The present invention is further described below by way of specific examples. The various chemical reagents used in the examples of the present invention are obtained through conventional commercial channels unless otherwise specified. Unless otherwise specified, the contents described below are all weight contents. Unless otherwise specified, it is understood that the process is carried out at room temperature.

[0027] Embodiment 1:

[0028] Embodiment 1 comprises the following steps:

[0029] Dissolve 1.5 g of dodecenylsuccinic anhydride in 200 mL of acetone, and stir at room temperature for 20 minutes; then add 1 g of nadic anhydride, and stir at room temperature for 20 minutes to obtain the first solution of Example 1;

[0030] 25 g of carbon black N330 was added to the first solution of Example 1, followed by stirring at room temperature for 2 hours, and then ultrasonicated at 40 kHz for 30 minutes to obtain a solution containing carbon black;

[0031] The solution containing carbon black in Example 1 was filtered to separate the carbon black and the acetone solution, and then the obtained carbon black was kept at 180° C. for 5 hours to obtain the modified carbon black in Example 1.

[0032] Embodiment 2:

[0033] Embodiment 2 comprises the following steps:

[0034] Dissolve 1.25 g of dodecenylsuccinic anhydride in 200 mL of acetone, and stir at room temperature for 20 minutes; then add 1.25 g of nadic anhydride, and stir at room temperature for 20 minutes to obtain the first solution of Example 2;

[0035] 25 g of carbon black N330 was added to the first solution of Example 2, followed by stirring at room temperature for 2 hours, and then ultrasonicated at 40 kHz for 30 minutes to obtain a solution containing carbon black;

[0036] The solution containing carbon black of Example 2 was filtered to separate the carbon black and the acetone solution, and then the obtained carbon black was kept at 180° C. for 5 hours to obtain the modified carbon black of Example 2.

[0037] Embodiment 3:

[0038] Embodiment 3 comprises the following steps:

[0039] 2 g of dodecenylsuccinic anhydride was dissolved in 200 mL of acetone, and the mixture was stirred at room temperature for 20 minutes; then 0.5 g of nadic anhydride was added, and the mixture was stirred at room temperature for 20 minutes to obtain the first solution of Example 3;

[0040] 25 g of carbon black N330 was added to the first solution of Example 3, followed by stirring at room temperature for 2 hours, and then ultrasonicated at 40 kHz for 30 minutes to obtain a solution containing carbon black;

[0041] The solution containing carbon black of Example 3 was filtered to separate the carbon black and the acetone solution, and then the obtained carbon black was kept at 180° C. for 5 hours to obtain the modified carbon black of Example 3.

[0042] Embodiment 4:

[0043] Embodiment 4 comprises the following steps:

[0044] Dissolve 0.5 g of dodecenylsuccinic anhydride in 200 mL of acetone, and stir at room temperature for 20 minutes; then add 2 g of nadic anhydride, and stir at room temperature for 20 minutes to obtain the first solution of Example 4;

[0045] 25 g of carbon black N330 was added to the first solution of Example 4, followed by stirring at room temperature for 2 hours, and then ultrasonicated at 40 kHz for 30 minutes to obtain a solution containing carbon black;

[0046] The solution containing carbon black of Example 4 was filtered to separate the carbon black and the acetone solution, and then the obtained carbon black was kept at 180° C. for 5 hours to obtain the modified carbon black of Example 4.

[0047] Embodiment 5:

[0048] Embodiment 5 comprises the following steps:

[0049] Dissolve 1 g of dodecenylsuccinic anhydride in 200 mL of acetone, and stir at room temperature for 20 minutes; then add 1.5 g of nadic anhydride, and stir at room temperature for 20 minutes to obtain the first solution of Example 5;

[0050] 25 g of carbon black N330 was added to the first solution of Example 4, followed by stirring at room temperature for 2 hours, and then ultrasonicated at 40 kHz for 30 minutes to obtain a solution containing carbon black;

[0051] The solution containing carbon black of Example 5 was filtered to separate the carbon black and the acetone solution, and then the obtained carbon black was kept at 180° C. for 5 hours to obtain the modified carbon black of Example 5.

[0052] Embodiment 6:

[0053] Embodiment 6 comprises the following steps:

[0054] Dissolve 1.5 g of dodecenylsuccinic anhydride in 200 mL of acetone, and stir at room temperature for 20 minutes; then add 1 g of nadic anhydride, and stir at room temperature for 20 minutes to obtain the first solution of Example 6;

[0055] 55 g of carbon black N330 was added to the first solution of Example 6, followed by stirring at room temperature for 2 hours, and then ultrasonicated at 40 kHz for 30 minutes to obtain a solution containing carbon black;

[0056] The solution containing carbon black of Example 6 was filtered to separate the carbon black and the acetone solution, and then the obtained carbon black was kept at 180°C for 5 hours to obtain the modified carbon black of Example 6.

[0057] Embodiment 7:

[0058] Embodiment 7 comprises the following steps:

[0059] 1.5 g of dodecenylsuccinic anhydride was dissolved in 200 mL of acetone, and the mixture was stirred at room temperature for 20 minutes; then 1 g of nadic anhydride was added, and the mixture was stirred at room temperature for 20 minutes to obtain the first solution of Example 7;

[0060] 18 g of carbon black N330 was added to the first solution of Example 7, followed by stirring at room temperature for 2 hours, and then ultrasonicated at 40 kHz for 30 minutes to obtain a solution containing carbon black;

[0061] The solution containing carbon black of Example 7 was filtered to separate the carbon black and the acetone solution, and then the obtained carbon black was kept at 180° C. for 5 hours to obtain the modified carbon black of Example 7.

[0062] Embodiment 8:

[0063] Embodiment 8 comprises the following steps:

[0064] Dissolve 2.5 g of dodecenylsuccinic anhydride in 200 mL of acetone and stir at room temperature for 20 minutes to obtain the first solution of Example 8;

[0065] 25 g of carbon black N330 was added to the first solution of Example 8, followed by stirring at room temperature for 2 hours, and then ultrasonicated at 40 kHz for 30 minutes to obtain a solution containing carbon black;

[0066] The solution containing carbon black of Example 8 was filtered to separate the carbon black and the acetone solution, and then the obtained carbon black was kept at 180° C. for 5 hours to obtain the modified carbon black of Example 8.

[0067] Embodiment 9:

[0068] Embodiment 9 comprises the following steps:

[0069] Dissolve 1.5 g of dodecenylsuccinic anhydride in 200 mL of acetone, and stir at room temperature for 20 minutes; then add 1 g of nadic anhydride, and stir at room temperature for 20 minutes to obtain the first solution of Example 1;

[0070] 25 g of carbon black N330 was added to the first solution of Example 9, followed by stirring at room temperature for 2 hours, and then ultrasonicated at 40 kHz for 30 minutes to obtain a solution containing carbon black;

[0071] The solution containing carbon black of Example 9 was filtered to separate the carbon black and the acetone solution, and then the obtained carbon black was kept at 180° C. for 5 hours to obtain the modified carbon black of Example 9.

[0072] Comparative Example 1:

[0073] Comparative Example 1 comprises the following steps:

[0074] Dissolve 2.5 g of maleic anhydride in 200 mL of acetone, and stir at room temperature for 20 minutes to obtain a first solution of Comparative Example 1;

[0075] 25 g of carbon black N330 was added to the first solution of Comparative Example 1, followed by stirring at room temperature for 2 hours, and then ultrasonicated at 40 kHz for 30 minutes to obtain a solution containing carbon black;

[0076] The solution containing carbon black of Comparative Example 1 was filtered to separate the carbon black and the acetone solution, and then the obtained carbon black was kept at 180° C. for 5 hours to obtain the modified carbon black of Comparative Example 1.

[0077] Comparative Example 2:

[0078] Comparative Example 2 comprises the following steps:

[0079] 1.5 g of maleic anhydride was dissolved in 200 mL of acetone and stirred at room temperature for 20 minutes; then 1 g of nadic anhydride was added and stirred at room temperature for 20 minutes to obtain the first solution of Comparative Example 2;

[0080] 25 g of carbon black N330 was added to the first solution of Comparative Example 2, followed by stirring at room temperature for 2 hours, and then ultrasonicated at 40 kHz for 30 minutes to obtain a solution containing carbon black;

[0081] The solution containing carbon black of Comparative Example 2 was filtered to separate the carbon black and the acetone solution, and then the obtained carbon black was kept at 180° C. for 5 hours to obtain the modified carbon black of Comparative Example 2.

[0082] Comparative Example 3:

[0083] Comparative Example 3 comprises the following steps:

[0084] 1.5 g of dodecenylsuccinic anhydride was dissolved in 200 mL of acetone, and the mixture was stirred at room temperature for 20 minutes; then 1 g of maleic anhydride was added, and the mixture was stirred at room temperature for 20 minutes to obtain the first solution of Comparative Example 3;

[0085] 25 g of carbon black N330 was added to the first solution of Comparative Example 3, followed by stirring at room temperature for 2 hours, and then ultrasonicated at 40 kHz for 30 minutes to obtain a solution containing carbon black;

[0086] The solution containing carbon black of Comparative Example 3 was filtered to separate the carbon black and the acetone solution, and then the obtained carbon black was kept at 180° C. for 5 hours to obtain the modified carbon black of Comparative Example 3.

[0087] Test 1: Dispersion stability test of Examples 1-9 and Comparative Examples 1-3

[0088] Weigh 0.15 g each of the modified carbon black prepared in Examples 1-9 and Comparative Examples 1-3, as well as carbon black N330, carbon black N220, and carbon black N234, add 30 mL of distilled water and ultrasonically disperse for 5 min, then pour them into test tubes respectively. After 48 h, take 1 mL of the supernatant and add 1 mL of distilled water into a 2 mL centrifuge tube. Centrifuge at 10000 r / min for 10 min. Use a syringe to aspirate the supernatant into a cuvette and measure the absorbance (wavelength = 510 nm). At the same time, observe the remaining dispersion in the test tube and measure the precipitation and stratification time. The test results are shown in Table 1.

[0089] Table 1

[0090] Example Dispersion stability Absorbance Example 1 60 days without delamination 0.625 Example 2 50 days stratification 0.601 Example 3 60 days stratification 0.611 Example 4 45 days stratification 0.594 Example 5 30 days stratification 0.582 Example 6 40 days stratification 0.564 Example 7 60 days without delamination 0.628 Example 8 50 days stratification 0.572 Example 9 50 days stratification 0.569 Comparative Example 1 30 days stratification 0.564 Comparative Example 2 35 days stratification 0.582 Comparative Example 3 35 days stratification 0.576 Carbon Black N330 2 days stratification 0.128 Carbon Black N220 1 day stratification 0.128 Carbon Black N234 3 days stratification 0.130

[0091] Test 2: Blackness test of Examples 1-9 and Comparative Examples 1-3:

[0092] According to GB / T 7048-2012 "Determination of the blackness of pigment carbon black", the blackness of the above Examples 1-9 and Comparative Examples 1-3 was tested, 0.2 g of the modified carbon black prepared in Examples 1-9 and Comparative Examples 1-3 were weighed respectively, mixed with refined No. 4 linseed oil respectively, and ground to obtain a uniform ink slurry, which was then coated into a film of uniform thickness, and the blackness value was measured using a reflectometer, and the My blackness value and the hue dM value were determined; the test results are shown in Table 2.

[0093] Table 2

[0094] Example My value dM value Example 1 298 15.4 Example 2 290 14.3 Example 3 292 13.5 Example 4 294 13.6 Example 5 288 12.4 Example 6 282 12.6 Example 7 297 15.0 Example 8 280 9.6 Example 9 292 12.9 Comparative Example 1 244 10.6 Comparative Example 2 270 11.2 Comparative Example 3 272 11.5

[0095] Among them, the higher My is, the higher the blackness of the carbon black is; dM represents the hue, when dM>0, it displays a blue phase, and when dM is less than 0, it displays a brown phase, that is, a red phase.

[0096] Those skilled in the art will readily appreciate other embodiments of the present disclosure after considering the specification and practicing the disclosure disclosed herein. The present disclosure is intended to cover any variations, uses, or adaptations of the present disclosure that follow the general principles of the present disclosure and include common knowledge or customary technical means in the art that are not disclosed in the present disclosure; the description and examples are to be regarded as exemplary only.

Claims

1. A method for preparing modified carbon black, characterized in that: The method comprises the following steps: Step 1: dissolving dodecenylsuccinic anhydride and nadic anhydride in an organic solvent to obtain a first solution; Step 2: adding carbon black to the first solution, stirring at room temperature for 1-3 hours, and then ultrasonicating for 5-60 minutes to obtain a solution containing a mixture; Step 3: Separating the solid and the solvent in the solution containing the mixture, and keeping the solid at 120° C.-200° C. for 3-8 hours to obtain the modified carbon black.

2. The preparation method according to claim 1, characterized in that: The mass ratio of the dodecenylsuccinic anhydride to the nadic anhydride is selected from (0.5-3):

1.

3. The preparation method according to claim 2, characterized in that: The mass ratio of the dodecenylsuccinic anhydride to the nadic anhydride is selected from (1.2-2):

1.

4. The preparation method according to claim 1, characterized in that: The ratio of the sum of the masses of the dodecenylsuccinic anhydride and the nadic anhydride to the mass of the carbon black is selected from (0.05-0.3):

1.

5. The preparation method according to claim 4, characterized in that: The ratio of the sum of the masses of the dodecenylsuccinic anhydride and the nadic anhydride to the mass of the carbon black is selected from (0.05-0.12):

1.

6. The preparation method according to claim 1, characterized in that: The organic solvent is selected from acetone.

7. A modified carbon black, characterized in that: The modified carbon black is prepared by the preparation method according to any one of claims 1 to 6.