CN117186671A - High-dispersibility modified carbon black and preparation method thereof - Google Patents
High-dispersibility modified carbon black and preparation method thereof Download PDFInfo
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- 239000006229 carbon black Substances 0.000 title claims abstract description 148
- 150000001721 carbon Chemical class 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 12
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- 238000000034 method Methods 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 16
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- 241000872198 Serjania polyphylla Species 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 238000005741 Steglich esterification reaction Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 11
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000004043 dyeing Methods 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000003086 colorant Substances 0.000 claims description 4
- 239000006232 furnace black Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000006231 channel black Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
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- 239000002245 particle Substances 0.000 abstract description 25
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 235000019241 carbon black Nutrition 0.000 description 116
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- CGQOFJKJTMICBC-UHFFFAOYSA-N 2-amino-6-methyl-1h-pyridin-4-one Chemical group CC1=CC(O)=CC(N)=N1 CGQOFJKJTMICBC-UHFFFAOYSA-N 0.000 description 1
- 101100481028 Arabidopsis thaliana TGA2 gene Proteins 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
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Abstract
The invention discloses a modified carbon black with high dispersibility and a preparation method thereof. According to the method, the surface of carbon black is modified by a liquid phase oxidation method, a reactive group carboxyl is introduced to the surface of the carbon black, and then a hydroxyl-terminated compound is grafted on the surface of oxidized carbon black by a Steglich esterification reaction, so that the modified carbon black with high dispersibility is prepared. The carbon black prepared by the invention can solve the problem that the carbon black is difficult to disperse in glycol solution, and ensures that the carbon black has good dispersibility in glycol. The maximum particle size of the modified carbon black prepared by the method in the glycol solution is only 142.3nm, and the PDI dispersion coefficient is only 0.032. The modified carbon black prepared by the method has better heat-resistant stability and placement stability, the stability can reach more than 96% after being heated for 2 hours at 120 ℃, and the stability can reach more than 95% after being placed for 10 days.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to modified carbon black with high dispersibility and a preparation method thereof.
Background
The polyester fiber is the first large variety of chemical fiber, while the black polyester fiber is the colored polyester fiber with the largest yield and dosage, and is widely applied to the fields of clothing fabric, home textile fabric, window shades, automobile interior trim and the like by virtue of the characteristics of high strength and modulus, good crease resistance and shape retention, fastness and durability, low water absorption, good light shielding property, low price and the like. Black polyesters are often obtained by pre-spin dope coloration and post-spin fiber-forming coloration. The dyeing after spinning is to dye the polyester fiber precursor, the color fastness of the colored fiber obtained by the method is poor, the discharge of dyeing and finishing wastewater and COD in the dyeing process is large, the pollution to the environment is serious, and the consumption of energy is large. Under the current era of low-carbon economy, energy conservation and emission reduction, the environment-friendly dyeing mode becomes a research hot spot. The dope is colored before spinning, that is, pigment or dye is added during the synthesis of the fiber, thereby directly obtaining colored fiber. The method disperses pigment or dye in the fiber, has high color fastness, saves the 'post dyeing and finishing' process for anhydrous coloring, saves energy consumption, reduces carbon dioxide emission, and belongs to an environment-friendly coloring method.
Carbon black has a wide range of applications as a good colorant and reinforcing agent, and has many advantages over other inorganic black pigments and black organic colorants, such as hiding power, color stability, solvent resistance, acid and alkali resistance, and thermal stability that are not comparable to other black pigments. Carbon black is an important black pigment used for coloring polyester fiber stock solution, aggregates with strong mechanical force are formed among carbon black particles in ethylene glycol in the process of coloring the polyester fiber stock solution, repulsive force among carbon black particles is small, and compatibility between the carbon black surface and the ethylene glycol is also small, so that stable and good ethylene glycol-based carbon black suspension system is difficult to obtain.
Because of the problems of easy agglomeration and difficult dispersion of carbon black, the problems of uneven dyeing, dull color and the like are easy to cause when the fiber is dyed or the fiber stock solution is dyed. Therefore, it is necessary to improve the dispersibility of carbon black and the dispersion stability in a medium. To improve the dispersion of carbon black in solution, the carbon black may be physically or chemically modified. Such as oxidative modification, graft modification, dispersant dispersion, grinding dispersion, etc., the application properties of the carbon black in use are improved by adding functional groups and functional polymers to the surface of the carbon black. As disclosed in patent CN110964349a, when hydrogen peroxide is used to oxidize carbon black, heteropolyacid is added, so that hydrophilic groups on the surface of carbon black are increased, and the carbon black has good dispersibility in water; patent CN108624090a discloses a method of grafting polyvinyl alcohol onto carbon black, the carbon black prepared by this method has good dispersibility in a polymer matrix; patent CN113549347a discloses a method for grafting ethylene-propylene-vinyl alcohol copolymer to carbon black, the dispersibility of the carbon black is improved, and the blackness is obviously improved when the carbon black is applied to an ink system, a coating system and a paint system. Although these methods all improve the dispersibility of carbon black in water, the dispersibility of the prepared modified carbon black in ethylene glycol is not ideal, thereby limiting the application of the modified carbon black in fiber dyeing.
Disclosure of Invention
The invention aims to develop nano carbon black with good dispersibility in a glycol system, so that the nano carbon black can meet the requirement of stock solution coloring of viscose fiber, lyocell fiber, polylactic acid fiber, polyamide fiber, polyester fiber and the like on the carbon black, and the problem of poor dispersion of the carbon black in glycol is solved.
In view of the above-mentioned object, the present invention provides a highly dispersible modified carbon black obtained by oxidizing and modifying carbon black with a liquid-phase oxidizing agent to obtain oxidized carbon black, then connecting the oxidized carbon black with a hydroxyl-terminated compound by a Steglich esterification reaction, and grafting a polymer chain on the carbon black surface.
In one embodiment of the present invention, the carbon black comprises one of furnace black, channel black, and pyrolysis black.
In one embodiment of the present invention, the liquid phase oxidizer comprises at least one of nitric acid, hydrogen peroxide, ammonium persulfate, and potassium permanganate solution.
In one embodiment of the present invention, the hydroxyl-terminated compound comprises at least one of ethylene glycol, polyethylene glycol 200, polyethylene glycol 600, polyethylene glycol 800, polyethylene glycol 1000.
In one embodiment of the present invention, the mass ratio of the hydroxyl-terminated compound to the oxidized carbon black is 0.1 to 3.
The invention also provides a preparation method of the modified carbon black, which comprises the following steps:
(1) Performing oxidation modification on carbon black by adopting a liquid-phase oxidant to obtain oxidized carbon black;
(2) Adding oxidized carbon black and hydroxyl-terminated compound into an organic solvent, dispersing, adding DMAP and DCC to obtain a mixed solution, reacting the mixed solution at 20-60 ℃ for 12-30 h, centrifuging at a high speed of 8000rmp for 20min, washing, drying at 100 ℃ for 2h, and grinding and crushing the dried powder to obtain the modified carbon black.
In one embodiment of the present invention, in the step (1), the ratio of the liquid-phase oxidizing agent to the carbon black is in the range of 5:1 to 20:1, the carbon black comprises one of furnace black, channel black and cracked black, and the liquid-phase oxidizing agent comprises at least one of nitric acid, hydrogen peroxide, ammonium persulfate and potassium permanganate solution.
In one embodiment of the present invention, in the step (1), the temperature at the time of oxidative modification is 50 to 100 ℃ for 2 to 8 hours.
In one embodiment of the present invention, in the step (2), the organic solvent is one of N, N-dimethylformamide, dichloromethane, and chloroform.
In one embodiment of the present invention, in the step (2), the dispersing manner includes magnetic stirring dispersing or ultrasonic dispersing, wherein the speed of the magnetic stirring is 20rpm, and the stirring time is 60min; the power during ultrasonic dispersion is 40Khz, and the ultrasonic treatment is carried out for 10-30 min.
In one embodiment of the present invention, in step (2), the mass fraction of the oxidized carbon black in the organic solvent after the dispersion is 1 to 40%, preferably 20 to 40%.
In one embodiment of the present invention, the DCC is added in an amount of 0.1 to 10%, preferably 5 to 10% by mass of the oxidized carbon black.
In one embodiment of the present invention, the DMAP is added in an amount of 1 to 10%, preferably 5 to 10% by mass of DCC.
The invention also provides application of the modified carbon black in the textile field.
In one embodiment of the invention, the application includes dyeing the fiber with a modified carbon black as a colorant or fiber stock.
The beneficial effects of the invention are that
(1) Introducing a reactive group carboxyl on the surface of carbon black by adopting a liquid-phase oxidation method, then reacting the carbon black with a hydroxyl compound through a Steglich esterification reaction, introducing a functional molecular chain on the surface of the carbon black, and filtering, washing and drying to prepare the modified carbon black. The method has the characteristics of simple production process, easy operation, high grafting rate and the like.
(2) The modified carbon black prepared by the method has better dispersibility in aqueous solution and higher dispersibility in glycol solution, the maximum particle size of the modified carbon black in glycol is only 142.3nm, and the PDI dispersion coefficient is only 0.032.
(3) The modified carbon black prepared by the method has better heat-resistant stability and placement stability, the heat-resistant stability of PEG200-OCB and PEG600-OCB is the best, and the stability is still more than 96% when heated for 2 hours at 120 ℃; the PEG800-OCB has the best storage (placement) stability, and the stability after being placed for 10 days is still more than 95%.
Drawings
FIG. 1 is an XRD pattern of the raw carbon black and oxidized carbon black of example 1;
FIG. 2 is an XPS full spectrum image of 4hOCB and virgin carbon black prepared in example 1;
FIG. 3 is a graph showing the peak separation of the 4hOCB produced in example 1 and the O element of the original carbon black;
FIG. 4 is a FESEM image of the original carbon black and the modified carbon black prepared in examples 2-4;
FIG. 5 is a graph showing the heat stability of oxidized carbon black 4hOCB and the prepared modified carbon black in ethylene glycol solution in examples 1-4.
FIG. 6 is a graph showing the stability of oxidized carbon black 4hOCB and the prepared modified carbon black in ethylene glycol solution in examples 1 to 4.
FIG. 7 is a thermogravimetric curve of the modified carbon blacks prepared in examples 1 to 4.
Detailed Description
In order that the technical content of the present invention may be more clearly understood, the following detailed description of the embodiments is given only for better understanding of the content of the present invention and is not intended to limit the scope of the present invention.
The testing method comprises the following steps:
heat resistance stability: taking 10mL of carbon black dispersion liquid, placing in a beaker, sealing, respectively preserving heat for 2 hours at 60, 70, 80, 90, 100 and 120 ℃, then taking the upper color paste, diluting by 1000 times by using ethylene glycol, testing the change of the carbon black particle size in the ethylene glycol color paste by using a Nano-ZS90 potential and particle size analyzer, and calculating the high temperature resistant stability S by using a formula T ：
Wherein d is 0 And d T The particle size of the dispersion before and after heating is nm.
Stability in storage: taking a certain amount of carbon black or oxidized carbon black, preparing into a 1% glycol-based carbon black dispersion liquid, standing for 14 days, diluting the upper layer solution of the carbon black or oxidized carbon black by using glycol for 1000 times at intervals, measuring the particle size change of the carbon black or oxidized carbon black by using a Nano-ZS90 potential and particle size analyzer, and calculating the storage stability Sc by using a formula:
wherein d0 and dc are the particle diameters of the dispersion before and after the dispersion is placed, respectively, in nm.
Thermal gravimetric curve test: 5mg of carbon black was taken in a crucible and their thermogravimetric curves were measured using a TGA2 fully automatic thermogravimetric analyzer under the test conditions N 2 Under the condition that the temperature is 40-800 ℃, the temperature rising rate is 10 ℃/min.
Example 1
1. Influence of the oxidation treatment time on the dispersibility of the oxidized carbon black in water.
4g of carbon black was treated with 20g of a nitric acid solution (65% strength) at 80℃and then centrifugally washed a plurality of times until the pH was 5, and dried and ground to obtain oxidized carbon black. Oxidized carbon blacks prepared at treatment times of 0, 2h, 4h, 6h and 8h were named as original CB, 2hOCB, 4hOCB, 6hOCB and 8hOCB, respectively, and the histories and Zeta potentials of the oxidized carbon blacks in aqueous solutions are shown in Table 1. As can be seen from Table 1, 4hOCB has the best dispersibility in aqueous solutions. XRD images of the original carbon black and oxidized carbon black are shown in FIG. 1, diffraction peaks appear at 24.37 degrees and 42.47 degrees of the original carbon black, and the positions of diffraction peaks of the OCB are consistent with those of the original carbon black, which shows that the oxidation does not seriously damage the main structure of the carbon black within the experimental set time.
As can be seen from fig. 2 and 3, the O element signal at the surface of the carbon black increases significantly after oxidation. The c=o and COO-ratios of the carbon black surface after oxidation increased significantly from 18.06% and 2.94% to 34.44% and 21.64% of CB.
TABLE 1 particle size and Zeta potential of the raw carbon black and oxidized carbon black in aqueous solution at various treatment times
| Sample of | Particle size/nm | Zeta potential/mV |
| Original CB | 6686 | -19.8 |
| 2hOCB | 167.2 | -22.3 |
| 4hOCB | 156.5 | -30.4 |
| 6hOCB | 162.1 | -34.2 |
| 8hOCB | 174.9 | -35.9 |
2. A preparation method of modified carbon black with high dispersibility comprises the following steps:
(1) Placing 4g of carbon black in 20g of nitric acid solution (the concentration is 65%), treating at 80 ℃ for 4 hours, centrifuging to separate the carbon black, cleaning until the pH is 5, and drying and grinding to obtain oxidized carbon black 4hOCB;
(2) 1g of 4hOCB and 2g of PEG600 are weighed, added into 40mL of N, N-dimethylformamide, dispersed for 10min by ultrasonic, then 1g of DCC and 0.1g of DMAP are added, the reaction system is transferred to a magnetic stirrer for reaction for 24h, and the modified carbon black PEG600-OCB is obtained by grinding and crushing the dried powder after filtering, washing and drying.
As can be seen from FIG. 4, the degree of aggregation of the modified carbon black PEG600-OCB in ethylene glycol is significantly reduced. The particle size of the modified carbon black PEG600-OCB in water is 172.9nm and the PDI is 0.137. The dispersion particle size in ethylene glycol was 132.1nm and the PDI was 0.091.
Example 2
Example 2 differs from example 1 in that in the preparation of the modified carbon black, 2g of PEG600 was replaced with 0.67g of PEG200 in step (2).
As can be seen from FIG. 4, the degree of aggregation of the modified carbon black PEG200-OCB in ethylene glycol is significantly reduced. Through tests, the particle size of the modified carbon black PEG200-OCB in ethylene glycol is 133.2nm, and the PDI is 0.096; the particle size in water was 194.1nm and the PDI was 0.164.
Example 3
Example 3 differs from example 1 in that in the preparation of the modified carbon black, 2g of PEG600 was replaced with 2.68g of PEG800 in step (2).
As can be seen from FIG. 4, the degree of aggregation of the modified carbon black PEG800-OCB in ethylene glycol is significantly reduced. Through testing, the particle size of the modified carbon black PEG800-OCB in ethylene glycol is 141.2nm, and the PDI is 0.071; the particle size in water was 172.9nm and the PDI was 0.137.
Example 4
Example 4 differs from example 1 in that in the preparation of the modified carbon black, 2g of PEG600 was replaced with 0.21g of ethylene glycol in step (2).
Through test, the particle size of EG-OCB in glycol is 142.3nm, and PDI is 0.032; the particle size in water was 204.7nm and the PDI was 0.201.
Fig. 5 to 7 show the heat stability curve, the storage stability (storage stability) curve, and the thermogravimetric curve of the oxidized carbon blacks 4 hccb and the modified carbon blacks prepared in examples 1 to 4, respectively. As can be seen from FIG. 5, the heat stability of PEG200-OCB and PEG600-OCB is best, and the stability is still more than 96% when heated at 120 ℃ for 2 hours. As can be seen from FIG. 6, the stability of the grafted carbon black is better than that of oxidized carbon black 4hOCB, wherein the PEG800-OCB has the best stability and the stability after 10d is still more than 95%. As can be seen in FIG. 7, the polymer has been successfully grafted onto the carbon black surface, and the grafted polymer has been decomposed mainly at 300-400 ℃.
Comparative example 1
The dispersibility in water and ethylene glycol solvents was tested directly using carbon black MA 100.
Through testing, the particle size of the carbon black MA100 in water is 66868 nm, and the PDI is 1; the particle size in ethylene glycol was 1261nm and the PDI was 1.
Comparative example 2
Comparative example 2 differs from example 1 in that step (1) was omitted in the preparation of the modified carbon black.
The particle size of the carbon black modified directly with polyethylene glycol without oxidation was 1832nm in water and 862.3nm in ethylene glycol.
Comparative example 3
Comparative example 3 differs from example 1 in that step (2) was omitted in the preparation of the modified carbon black.
The particle size of the oxidized carbon black in water was tested to be 156.5nm and in ethylene glycol was tested to be 225nm.
Comparative example 4
Comparative example 4 differs from example 1 in that in the preparation of the modified carbon black, PEG600 was replaced with 2-amino-4-hydroxy-6-methylpyridine in step (2).
The particle size of the modified carbon black in water was 284.8nm and in ethylene glycol was 182.3nm.
Claims (10)
1. A modified carbon black with high dispersibility is characterized in that the modified carbon black is obtained by oxidizing and modifying carbon black by adopting a liquid-phase oxidizing agent to obtain oxidized carbon black, connecting the oxidized carbon black with a hydroxyl-terminated compound through a Steglich esterification reaction, and grafting a high molecular chain on the surface of the carbon black.
2. The modified carbon black of claim 1, wherein the carbon black comprises one of furnace black, channel black, cracked black, and the liquid phase oxidizer comprises at least one of nitric acid, hydrogen peroxide, ammonium persulfate, potassium permanganate solution.
3. The modified carbon black according to claim 1, wherein the hydroxyl-terminated compound comprises at least one of ethylene glycol, polyethylene glycol 200, polyethylene glycol 600, polyethylene glycol 800, polyethylene glycol 1000, and the mass of the hydroxyl-terminated compound and oxidized carbon black is 0.1 to 3.
4. A method for producing the modified carbon black of high dispersibility according to any one of claims 1 to 3, comprising the steps of:
(1) Performing oxidation modification on carbon black by adopting a liquid-phase oxidant to obtain oxidized carbon black;
(2) Adding oxidized carbon black and hydroxyl-terminated compound into an organic solvent, dispersing, adding DMAP and DCC to obtain a mixed solution, reacting the mixed solution at 20-60 ℃ for 12-30 h, centrifuging at a high speed of 8000rmp for 20min, washing, drying at 100 ℃ for 2h, and grinding and crushing the dried powder to obtain the modified carbon black.
5. The method according to claim 4, wherein in the step (1), the ratio of the liquid-phase oxidizing agent to the carbon black is in the range of 5:1 to 20:1, the carbon black comprises one of furnace black, tank black and cracked black, the liquid-phase oxidizing agent comprises at least one of nitric acid, hydrogen peroxide, ammonium persulfate and potassium permanganate solution, the temperature during the oxidative modification is 50 to 100 ℃ and the time is 2 to 8 hours.
6. The method according to claim 4, wherein in the step (2), the organic solvent is one of N, N-dimethylformamide, dichloromethane and chloroform, and the dispersing means comprises magnetic stirring dispersing or ultrasonic dispersing.
7. The method according to claim 4, wherein in the step (2), the mass fraction of the oxidized carbon black in the organic solvent after the dispersion is 1 to 40%.
8. The method according to claim 4, wherein the DCC is added in an amount of 0.1 to 10% by mass of the oxidized carbon black and the DMAP is added in an amount of 1 to 10% by mass of the DCC.
9. Use of the modified carbon black of any one of claims 1 to 3 in the textile field.
10. The use according to claim 9, characterized in that it comprises dyeing the fibres with modified carbon black as a colorant or dyeing the fibres in stock.
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2023
- 2023-08-21 CN CN202311055468.6A patent/CN117186671A/en active Pending
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