CN116715583A - Super-dispersant special for carbon black and carbon black masterbatch prepared by using super-dispersant - Google Patents
Super-dispersant special for carbon black and carbon black masterbatch prepared by using super-dispersant Download PDFInfo
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- CN116715583A CN116715583A CN202310589199.5A CN202310589199A CN116715583A CN 116715583 A CN116715583 A CN 116715583A CN 202310589199 A CN202310589199 A CN 202310589199A CN 116715583 A CN116715583 A CN 116715583A
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- 239000006229 carbon black Substances 0.000 title claims abstract description 112
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 34
- 239000002270 dispersing agent Substances 0.000 title description 8
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 11
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims abstract description 11
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011276 wood tar Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011347 resin Substances 0.000 claims description 28
- 229920005989 resin Polymers 0.000 claims description 28
- LXNOENXQFNYMGT-UHFFFAOYSA-N xi-5-Hydroxydodecanoic acid Chemical compound CCCCCCCC(O)CCCC(O)=O LXNOENXQFNYMGT-UHFFFAOYSA-N 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 abstract description 17
- 239000002245 particle Substances 0.000 abstract description 13
- 239000006185 dispersion Substances 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- -1 5-hydroxydodecanol ester Chemical class 0.000 abstract description 2
- 239000012736 aqueous medium Substances 0.000 abstract description 2
- 239000004595 color masterbatch Substances 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000000049 pigment Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 238000004873 anchoring Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- AOJJSUZBOXZQNB-VTZDEGQISA-N 4'-epidoxorubicin Chemical group O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-VTZDEGQISA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- CRGUYVKXAVIZEB-UHFFFAOYSA-N dodecane-1,5-diol Chemical compound CCCCCCCC(O)CCCCO CRGUYVKXAVIZEB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical group C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and relates to a special hyperdispersant for carbon black and a carbon black masterbatch prepared by using the hyperdispersant. The invention discloses a special hyperdispersant for carbon black, which is prepared by heating purified 5-hydroxydodecanol ester, pyroligneous acid, mercaptoethanol and peroxydicarbonate at 110-130 ℃, and continuously stirring in the heating process. The invention also discloses a carbon black masterbatch, which comprises the components of the hyperdispersant special for carbon black. The invention also discloses application of the carbon black masterbatch in a high polymer material. The special hyperdispersant for the carbon black is prepared by reacting 5-hydroxydodecanoyl glyceride and wood-tar acid through a one-step method, can reduce the inter-particle attraction in a dispersion system, and increases the dispersion stability of solid particles in a non-aqueous medium; the thickness of the adsorption layer is larger, so that the hyperdispersant is not desorbed from the particle surface, and the aggregation phenomenon is avoided; the dispersibility of the carbon black in the ABS resin carrier is improved.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a special hyperdispersant for carbon black and a carbon black masterbatch prepared by using the hyperdispersant.
Background
The hyper-dispersant is a high-efficiency polymer type dispersing auxiliary agent, and is widely applied to industries such as paints, inks and the like at home and abroad. The molecular structure of the hyperdispersant is divided into two parts: one part is an anchoring group which can be tightly adsorbed on the surface of pigment particles to prevent the hyperdispersant from being desorbed; the other part is a solvated chain which has good compatibility with a dispersion medium and can form a protective layer with enough thickness on the surface of the pigment. When the pigment particles adsorbed with the hyperdispersant are close to each other, the particles are sprung apart due to the interaction between the protective layers, thereby achieving stable dispersion of the pigment particles in the medium.
Carbon black is used as a common coloring source in color master batches, but the dispersibility of the carbon black in the color master batches is poor due to the small primary particle size, low volatile matters and difficult dispersion; there is therefore a need for new methods to ameliorate the above-mentioned drawbacks.
Disclosure of Invention
The invention aims at solving the problems in the prior art and provides a special hyperdispersant for carbon black, which is prepared by reacting 5-hydroxydodecanoyl glyceride and wood-tar acid in one step and can effectively improve the dispersibility of carbon black in carrier resin.
The aim of the invention can be achieved by the following technical scheme:
a hyperdispersant special for carbon black is prepared by heating purified 5-hydroxydodecanoate, pyroligneous acid, mercaptoethanol and peroxydicarbonate at 110-130 ℃, and continuously stirring in the heating process.
According to the invention, 5-hydroxydodecanoyl glyceride is selected as an anchoring section, so that the chain length is increased, and the 5-hydroxydodecanoyl glyceride has higher affinity to a solvent and good solvation and dissolution properties; in addition, 5-hydroxydodecanoyl glyceride has OH - 、COO - Two anchoring groups tightly suck the hyper-dispersant on the surface of the pigment in a multi-point anchoring mode. And the solvent layer thickness is increased by using the wooden pyrooleic acid as a solvation chain and the wooden pyrooleic acid and the 5-hydroxydodecanol ester react to form a superimposed lamellar structure, so that the thickness of the adsorption layer of the obtained hyper-dispersant is larger than that of other hyper-dispersants, and the obvious space barrier effect is achieved.
Preferably, the parts ratio of 5-hydroxydodecanoate, wood pyrooleic acid, mercaptoethanol and peroxydicarbonate is (50-70): (40-65): (5-10): (4-8).
Further preferably, the part ratio of 5-hydroxydodecanoyl glyceride and wood-tar acid is (1-1.6): 1.
preferably, the molecular formula of the hyperdispersant special for carbon black is C 39 H 76 O 6 The molecular structure is as follows:
the invention also discloses a carbon black masterbatch, which comprises the components of the hyperdispersant special for carbon black.
Preferably, the carbon black masterbatch comprises the following components in parts by weight: 50-90 parts of first carrier resin, 50-90 parts of second carrier resin, 20-40 parts of carbon black, 5-20 parts of carbon black special hyperdispersant and 1-5 parts of other auxiliary agents.
Further preferably, the mass ratio of the first carrier resin to the second carrier resin is (0.8 to 1.5): 1.
still more preferably, the first carrier resin is a PA757 type ABS; the second carrier resin is a PA737 type ABS.
Further preferably, the mass ratio of the carbon black to the hyperdispersant special for the carbon black is (2-6): 1.
more preferably, the proportion of the hyperdispersant special for carbon black is 5-12%.
The invention also discloses application of the carbon black masterbatch in a high polymer material.
Preferably, the polymeric material includes, but is not limited to PP, PE, PS, PVC.
Compared with the prior art, the invention has the following beneficial effects:
the special hyperdispersant for the carbon black is prepared by reacting 5-hydroxydodecanoyl glyceride and wood-tar acid through a one-step method, can reduce the inter-particle attraction in a dispersion system, and increases the dispersion stability of solid particles in a non-aqueous medium; the thickness of the adsorption layer is larger, so that the hyperdispersant is not desorbed from the particle surface, and the aggregation phenomenon is avoided; the dispersibility of the carbon black in the ABS resin carrier is improved.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention are further described, but the present invention is not limited to these examples.
Example 1
Preparing a hyperdispersant special for carbon black:
purifying the 5-hydroxydodecanoate, magnetically stirring the purified 64 parts of the 5-hydroxydodecanoate with 51 parts of wood pyrooleic acid, 8 parts of mercaptoethanol and 7 parts of peroxydicarbonate for 3 hours at 120 ℃, cooling to room temperature, filtering under reduced pressure, washing with acetone and absolute ethanol for 3 times, and drying to obtain the special hyperdispersant for carbon black.
Preparing carbon black masterbatch:
placing 27 parts of carbon black and 13 parts of special hyperdispersant for carbon black into a high-speed mixer to mix for 10min to obtain pre-dispersed carbon black; the pre-dispersed carbon black is added into a torque rheometer together with 77 parts of first carrier resin (PA 757 type ABS), 78 parts of second carrier resin (PA 737 type ABS resin) and 5 parts of lubricant, and the mixture is mixed at 220 ℃ to obtain pre-dispersed color master batch, and the pre-dispersed color master batch is placed into a double screw extruder at 130 ℃ to be extruded and granulated to obtain the carbon black color master batch.
The tensile strength of the obtained carbon black masterbatch is 49Mpa, and the impact strength is 8.5KJ/m 2 The dispersibility was 76% and the blackness was 80.
Example 2
Preparing a hyperdispersant special for carbon black:
purifying 5-hydroxydodecanoate, magnetically stirring 70 parts of purified 5-hydroxydodecanoate, 50 parts of wood pyrooleic acid, 5 parts of mercaptoethanol and 5 parts of peroxydicarbonate for 3 hours at 120 ℃, cooling to room temperature, filtering under reduced pressure, washing with acetone and absolute ethanol for 3 times, and drying to obtain the special hyperdispersant for carbon black.
Preparing carbon black masterbatch:
putting 36 parts of carbon black and 45 parts of special hyperdispersant for carbon black into a high-speed mixer to mix for 10min to obtain pre-dispersed carbon black; the pre-dispersed carbon black is added into a torque rheometer together with 70 parts of a first carrier resin (PA 757 type ABS), 78 parts of a second carrier resin (PA 737 type ABS resin) and 4 parts of a lubricant, the mixture is mixed at 220 ℃ to obtain pre-dispersed color master batches, and the pre-dispersed color master batches are placed into a double-screw extruder at 130 ℃ to be extruded and granulated to obtain the carbon black color master batches.
Stretching of the obtained carbon black masterbatchThe strength is 47Mpa, and the impact strength is 8.3KJ/m 2 The dispersibility was 75% and the blackness was 88.
Example 3
Preparing a hyperdispersant special for carbon black:
purifying 5-hydroxydodecanoate, magnetically stirring 66 parts of purified 5-hydroxydodecanoate, 53 parts of wood pyrooleic acid, 6 parts of mercaptoethanol and 5 parts of peroxydicarbonate for 3 hours at 120 ℃, cooling to room temperature, filtering under reduced pressure, washing with acetone and absolute ethanol for 3 times, and drying to obtain the special hyperdispersant for carbon black.
Preparing carbon black masterbatch:
mixing 40 parts of carbon black and 18 parts of a special hyperdispersant for carbon black in a high-speed mixer for 10min to obtain pre-dispersed carbon black; adding pre-dispersed carbon black, 80 parts of a first carrier resin (PA 757 type ABS), 60 parts of a second carrier resin (PA 737 type ABS resin) and 2 parts of a lubricant into a torque rheometer, mixing at 220 ℃ to obtain pre-dispersed color master batch, and placing the pre-dispersed color master batch into a double screw extruder at 130 ℃ for extrusion granulation to obtain the carbon black color master batch.
The tensile strength of the obtained carbon black masterbatch is 42Mpa, and the impact strength is 7.1KJ/m 2 The dispersibility was 80% and the blackness was 83.
Example 4
Compared with example 1, the preparation of the hyperdispersant special for carbon black is different:
purifying 5-hydroxydodecanoyl glyceride, magnetically stirring 60 parts of purified 5-hydroxydodecanoyl glyceride, 60 parts of wood pyrooleic acid, 5 parts of mercaptoethanol and 5 parts of peroxydicarbonate for 3 hours at 120 ℃, cooling to room temperature, filtering under reduced pressure, washing with acetone and absolute ethanol for 3 times, and drying to obtain the special hyperdispersant for carbon black.
The tensile strength of the obtained carbon black masterbatch is 45Mpa, and the impact strength is 7.8KJ/m 2 The dispersibility was 74% and the blackness was 78.
Example 5
Compared with example 1, the preparation of the hyperdispersant special for carbon black is different:
purifying 5-hydroxydodecanoate, magnetically stirring 50 parts of purified 5-hydroxydodecanoate, 67 parts of wood pyrooleic acid, 8 parts of mercaptoethanol and 5 parts of peroxydicarbonate for 3 hours at 120 ℃, cooling to room temperature, filtering under reduced pressure, washing with acetone and absolute ethanol for 3 times, and drying to obtain the special hyperdispersant for carbon black.
The tensile strength of the obtained carbon black masterbatch is 43Mpa, and the impact strength is 7.6KJ/m 2 The dispersibility was 68% and the blackness was 69.
In this example, the ratio of 5-hydroxydodecanoate to wood-tar is out of range, and wood-tar is too high, resulting in too high affinity for solvents, and easy desorption, resulting in pigment aggregation, and further resulting in reduced dispersibility and blackness of the carbon black masterbatch.
Example 6
Compared with example 1, the preparation of the hyperdispersant special for carbon black is different:
purifying 5-hydroxydodecanoyl glyceride, magnetically stirring the purified 72 parts of 5-hydroxydodecanoyl glyceride, 40 parts of wood-tar acid, 10 parts of mercaptoethanol and 8 parts of peroxydicarbonate for 3 hours at 120 ℃, cooling to room temperature, decompressing, filtering, washing with acetone and absolute ethanol for 3 times, and drying to obtain the special hyperdispersant for carbon black.
The tensile strength of the obtained carbon black masterbatch is 44Mpa, and the impact strength is 7.9KJ/m 2 The dispersibility was 67% and the blackness was 70%.
In this example, the ratio of 5-hydroxydodecanoate to wood-tar is out of range, and wood-tar is too small, which results in poor dimensional stability, too close particles, and easy agglomeration of pigment, and further results in reduced dispersibility and blackness of the carbon black masterbatch.
Example 7
In comparison with example 1, the difference is in the preparation of carbon black masterbatch:
mixing 40 parts of carbon black and 18 parts of a special hyperdispersant for carbon black in a high-speed mixer for 10min to obtain pre-dispersed carbon black; the pre-dispersed carbon black is added into a torque rheometer together with 90 parts of a first carrier resin (PA 757 type ABS), 50 parts of a second carrier resin (PA 737 type ABS resin) and 2 parts of a lubricant, the mixture is mixed at 220 ℃ to obtain pre-dispersed color master batches, and the pre-dispersed color master batches are placed into a double-screw extruder at 130 ℃ to be extruded and granulated to obtain the carbon black color master batches.
The tensile strength of the obtained carbon black masterbatch is 41Mpa, and the impact strength is 6.9KJ/m 2 The dispersibility was 81% and the blackness was 77.
In this embodiment, the mass ratio of the first carrier resin to the second carrier resin is out of range, which results in uneven mixing of the two, and easy agglomeration during processing, resulting in reduced mechanical properties of the color master batch.
Example 8
In comparison with example 1, the difference is in the preparation of carbon black masterbatch:
50 parts of carbon black and 8 parts of special hyperdispersant for carbon black are placed in a high-speed mixer to be mixed for 10min, so as to obtain pre-dispersed carbon black; the pre-dispersed carbon black is added into a torque rheometer together with 92 parts of a first carrier resin (PA 757 type ABS), 47 parts of a second carrier resin (PA 737 type ABS resin) and 3 parts of a lubricant, the mixture is mixed at 220 ℃ to obtain pre-dispersed color master batches, and the pre-dispersed color master batches are placed into a double-screw extruder at 130 ℃ to be extruded and granulated to obtain the carbon black color master batches.
The tensile strength of the obtained carbon black masterbatch is 40Mpa, and the impact strength is 6.8KJ/m 2 The dispersibility was 65% and the blackness was 69.
In the embodiment, the proportion of the hyperdispersant special for the carbon black is relatively low, and the proportion of the second carrier resin in the first carrier resin and the second carrier resin is relatively large, so that the dispersibility is influenced, and the mechanical property is influenced to a certain extent.
Comparative example 1
The carbon black master batch was prepared as described in example 1 using a hyperdispersant of the AKN-2210 type produced by Qianli chemical Co., ltd.
The tensile strength of the obtained carbon black masterbatch is 42Mpa, and the impact strength is 6KJ/m 2 The dispersibility was 69% and the blackness was 71.
Comparative example 2
The difference compared with example 1 is that no hyperdispersant special for carbon black is added;
preparing carbon black masterbatch:
26 parts of carbon black, 77 parts of first carrier resin (PA 757 type ABS), 78 parts of second carrier resin (PA 737 type ABS resin) and 17 parts of lubricant are added into a torque rheometer and mixed at 220 ℃ to obtain pre-dispersed color master batch, and the pre-dispersed color master batch is placed into a double screw extruder at 130 ℃ to be extruded and granulated to obtain the carbon black color master batch.
The tensile strength of the obtained carbon black masterbatch is 38Mpa, and the impact strength is 5.2KJ/m 2 The dispersibility was 55% and the blackness was 65.
In conclusion, the special hyperdispersant for the carbon black is prepared by reacting 5-hydroxydodecanol and pyroligneous acid in one step, can reduce the inter-particle attraction in a dispersion system, increases the dispersion stability of solid particles in a nonaqueous medium, and improves the dispersibility of the carbon black in an ABS resin carrier.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (10)
1. A special hyperdispersant for carbon black is characterized in that the special hyperdispersant for carbon black is prepared by heating 5-hydroxydodecanoyl glyceride, pyroligneous acid, mercaptoethanol and peroxydicarbonate at 110-130 ℃, and stirring continuously in the heating process.
2. The special hyperdispersant for carbon black according to claim 1, wherein the parts ratio of 5-hydroxydodecanoate, pyroligneous acid, mercaptoethanol and peroxydicarbonate is (50-70): (40-65): (5-10): (4-8).
3. The hyperdispersant special for carbon black according to claim 2, wherein the parts ratio of 5-hydroxydodecanoate to wood-tar acid is (1-1.6): 1.
4. the hyperdispersant for carbon black as claimed in claim 1, wherein the molecular formula of the hyperdispersant for carbon black is C 39 H 76 O 6 The molecular structure is as follows:
5. a carbon black masterbatch, comprising the carbon black-specific hyperdispersant of claim 1.
6. The carbon black masterbatch according to claim 5, wherein the components of the carbon black masterbatch, in parts by weight, comprise: 50-90 parts of first carrier resin, 50-90 parts of second carrier resin, 20-40 parts of carbon black, 5-20 parts of carbon black special hyperdispersant and 1-5 parts of other auxiliary agents.
7. The carbon black masterbatch according to claim 6, wherein the mass ratio of the first carrier resin to the second carrier resin is (0.8 to 1.5): 1.
8. the carbon black masterbatch according to claim 6, wherein the mass ratio of the carbon black to the hyperdispersant for the carbon black is (2-6): 1.
9. the carbon black masterbatch according to claim 6, characterized in that the proportion of the hyperdispersant dedicated to carbon black is 5-12%.
10. The use of the carbon black masterbatch according to claim 5 in polymeric materials.
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| CN202310589199.5A CN116715583A (en) | 2023-05-24 | 2023-05-24 | Super-dispersant special for carbon black and carbon black masterbatch prepared by using super-dispersant |
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