CN111171607B - A kind of method for preparing hydrophilic carbon black, hydrophilic carbon black and application thereof - Google Patents
A kind of method for preparing hydrophilic carbon black, hydrophilic carbon black and application thereof Download PDFInfo
- Publication number
- CN111171607B CN111171607B CN201911407274.1A CN201911407274A CN111171607B CN 111171607 B CN111171607 B CN 111171607B CN 201911407274 A CN201911407274 A CN 201911407274A CN 111171607 B CN111171607 B CN 111171607B
- Authority
- CN
- China
- Prior art keywords
- carbon black
- rubber
- hypochlorite
- hydrophilic
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000006229 carbon black Substances 0.000 title claims abstract description 214
- 238000000034 method Methods 0.000 title claims abstract description 45
- 229920001971 elastomer Polymers 0.000 claims abstract description 82
- 239000005060 rubber Substances 0.000 claims abstract description 82
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000006185 dispersion Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 12
- 241000872198 Serjania polyphylla Species 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000010521 absorption reaction Methods 0.000 claims description 15
- 244000043261 Hevea brasiliensis Species 0.000 claims description 14
- 229920003052 natural elastomer Polymers 0.000 claims description 14
- 229920001194 natural rubber Polymers 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229920000126 latex Polymers 0.000 claims description 11
- 239000004816 latex Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000001179 sorption measurement Methods 0.000 claims description 11
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 10
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 10
- 229920005549 butyl rubber Polymers 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 9
- 239000004636 vulcanized rubber Substances 0.000 claims description 9
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 2
- 229920000459 Nitrile rubber Polymers 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- KBKZYWOOZPIUJT-UHFFFAOYSA-N azane;hypochlorous acid Chemical compound N.ClO KBKZYWOOZPIUJT-UHFFFAOYSA-N 0.000 claims description 2
- HPEWZLCIOKVLBZ-UHFFFAOYSA-N barium hypochlorite Chemical compound [Ba+2].Cl[O-].Cl[O-] HPEWZLCIOKVLBZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- HLUYHVRRGFKTTM-UHFFFAOYSA-N copper(1+);hypochlorite Chemical compound [Cu+].Cl[O-] HLUYHVRRGFKTTM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims description 2
- YZQBYALVHAANGI-UHFFFAOYSA-N magnesium;dihypochlorite Chemical compound [Mg+2].Cl[O-].Cl[O-] YZQBYALVHAANGI-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 238000004898 kneading Methods 0.000 claims 1
- 229920006173 natural rubber latex Polymers 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 36
- 230000003647 oxidation Effects 0.000 abstract description 29
- 238000002156 mixing Methods 0.000 abstract description 7
- 238000007906 compression Methods 0.000 abstract description 5
- 230000006835 compression Effects 0.000 abstract description 5
- 238000005096 rolling process Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 235000019241 carbon black Nutrition 0.000 description 190
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 18
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 17
- 239000007791 liquid phase Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- 238000011160 research Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 235000021355 Stearic acid Nutrition 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 9
- 239000008117 stearic acid Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 238000004073 vulcanization Methods 0.000 description 9
- 239000011787 zinc oxide Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000002715 modification method Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000011033 desalting Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000006232 furnace black Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010073 coating (rubber) Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- OXCRJCXSFXJLFS-UHFFFAOYSA-N zinc;dihypochlorite Chemical compound [Zn+2].Cl[O-].Cl[O-] OXCRJCXSFXJLFS-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
- C09C1/50—Furnace black ; Preparation thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
本发明公开了一种制备亲水性炭黑的方法，包括如下步骤：(1)将炉法炭黑与次氯酸盐水溶液混合，反应得到炭黑分散液；(2)将步骤(1)所得的炭黑分散液经过固液分离、烘干得到亲水性炭黑。使用此方法的优点在于该条件下的次氯酸盐氧化后的炭黑不需要进一步分级、纯化处理，从而简化生产工艺，降低成本，保护环境。亲水性炭黑加入橡胶后，使得橡胶提高了断裂伸长率，降低了滚动阻力和压缩疲劳温升。The invention discloses a method for preparing hydrophilic carbon black, comprising the following steps: (1) mixing furnace carbon black with an aqueous hypochlorite solution, and reacting to obtain a carbon black dispersion; The obtained carbon black dispersion is subjected to solid-liquid separation and drying to obtain hydrophilic carbon black. The advantage of using this method is that the carbon black after hypochlorite oxidation under this condition does not need to be further classified and purified, thereby simplifying the production process, reducing costs and protecting the environment. The addition of hydrophilic carbon black to the rubber increases the elongation at break and reduces the rolling resistance and compression fatigue temperature rise.
Description
Technical Field
The invention relates to preparation of hydrophilic carbon black and application of the hydrophilic carbon black in rubber, in particular to a method for preparing carbon black dispersion liquid by reacting furnace carbon black with hypochlorite aqueous solution, obtaining hydrophilic carbon black by centrifugal separation and drying, and applying the prepared hydrophilic carbon black in rubber.
Background
Carbon black is one of important industrial raw materials, and has characteristics of good weather resistance, chemical stability, colorability, conductivity and the like, so that carbon black is widely used in industrial fields such as rubber, paint, ink, printing and dyeing.
The carbon black has small particle size, large specific surface area and strong intermolecular force, so the carbon black is easy to agglomerate; at the same time, since the carbon black has a small number of oxygen-containing functional groups (carboxyl groups, hydroxyl groups, etc.) on the surface thereof and is hydrophobic and has low wettability, it is extremely difficult to stably disperse the carbon black in water at a high concentration, which affects the application of the carbon black in the industrial fields of ink, printing and dyeing, etc.
The method for improving the dispersion stability of the carbon black in water comprises the following steps: direct dispersion method, graft modification method, surface coating method and oxidation modification method.
The direct dispersion method is a method in which a dispersant and carbon black are mixed in water and the carbon black is dispersed under the action of a suitable external force. Although the direct dispersion method is simple to operate and easy to control conditions, the dispersion system can generate the phenomenon of inverse coarseness along with the increase of time, and the use of the product is not facilitated.
The graft modification method is to graft a polymer on the surface of carbon black through a chemical bond, and a certain steric hindrance repulsion is provided due to the long chain of the polymer. However, the use of the graft modification method is related to the type of carbon black, and the graft modification method has complex process flow and higher requirements on process conditions, and is difficult to be widely applied in industry.
The surface coating method is to coat a layer of hydrophilic polymer on the surface of the carbon black so that the carbon black can be stably dispersed in water. The surface coating method is independent of the type of carbon black, but the steps are complicated, and the industrial popularization is difficult.
The oxidation modification method is classified into a liquid-phase oxidation method, a gas-phase oxidation method, a plasma oxidation method, and a metal catalytic oxidation method.
The liquid phase oxidation method is a method of obtaining hydrophilic carbon black by subjecting carbon black and a strong oxidizing agent to oxidation-reduction reaction in water to form oxygen-containing functional groups such as hydrophilic carboxyl groups, carbonyl groups, hydroxyl groups, and the like on the surface of carbon black having a small volatile content.
The gas-phase oxidation method selects a gas-phase oxidant (mainly oxygen, air, ozone, oxynitride and the like) to oxidize and modify the surface of the carbon black, and is one of the traditional carbon black oxidation methods in industry.
The plasma oxidation method mainly comprises three types of microwave plasma, radio frequency plasma and arc plasma. Although the plasma oxidation method has a great development prospect in industrial production, the research on how to uniformly oxidize carbon black in a reaction vessel and how to reduce energy consumption is still the focus of the current stage.
The metal catalytic oxidation method is a method of catalytically oxidizing ordinary carbon black with a catalyst such as a metal chloride, a metal oxide, or a nitrogen oxide. At present, the method is still in a laboratory stage and is not industrialized.
In summary, liquid phase oxidation is a fast and efficient method for modifying carbon black. The liquid phase oxidation method, which is the earliest Surface oxidation modification method used in the carbon black industry, is widely reported in the literature, and the Oxidizing agent used is generally a strongly Oxidizing solution, such as nitric acid solution (Trawczy ń ski J, Japan S, Sayag C, et al. Surface acid of the activated CBC [ J ]. Fuel Processing Technology, 2002, 77-78: 317. 324.), sulfuric acid solution (Borah D, Satokawa S, Kato S, et al. Classification of chemical Modified carbon black for use in the application [ J ]. Applied Surface Science,2008, 3049. 3056), perchloric acid solution (Module J, Bureakicz-Momoc W, Janic M, Change 254, molecular of molecular, molecular of research 254, Journal of research of the company J, molecular of research, molecular research of molecular research, molecular research of molecular research, molecular research of research, research of molecular research of research, xinyu, Bozhongwei, hydrogen peroxide oxidation preparation of highly dispersible carbon black [ J ], silicate report, 2008, 27(6): 1124-: 78-84), diazonium salts (U.S. Pat. No.5,630,868, U.S. Pat. No.5,672,198), and the like. Of course, the physical properties of carbon blacks obtained by different oxidizing agents and different production methods vary due to different oxidizing effects. After oxidation, the oxygen-containing groups on the surface of the carbon black are increased, the wettability of the carbon black with water is improved, and a stable water-based carbon black dispersion system is easily obtained.
US2439442, US668724 disclose a process for treating carbon black with hypochlorite, which carbon black is acidified with hydrochloric acid to obtain a hydrophilic carbon black paste.
US3347632 discloses a process for treating carbon black with sodium hypochlorite which requires that the carbon black have an average particle size of less than 100nm, otherwise the treated carbon black is not dispersible in water.
US5609671, JPH107968, discloses a method of treating commercial acidic carbon black (preferably pH <4) with hypochlorite as an aqueous pigment ink, preferably at a temperature of 95 ℃ to 105 ℃ for a time of preferably 10 to 15 hours, which requires reverse osmosis membrane desalination until the conductivity of the dispersion becomes 0.2 mS/cm.
US5718746 discloses a process for treating low oil absorption carbon black (oil absorption <100ml/100g) with 1.6mol/L hypochlorite as an aqueous pigment ink, preferably at a temperature of 95 ℃ to 105 ℃ for a time of 3 to 20 hours, and requiring desalting and purification of the carbon black with an ultrafiltration membrane.
US7220304 discloses a process for using 1.6mol/L hypochlorite-treated carbon black as a water-based ink, the dispersion/pulverization step is carried out while oxidizing at a temperature of preferably 40 to 60 c for a time of preferably 3 to 10 hours at a dispersion/pulverization rotation speed of at least 500 rpm. Desalting and purification are carried out by using an ultrafiltration membrane, and secondary desalting and purification are carried out by using an electrodialyzer until the electrical conductivity of the filtrate is not more than 1.5 mS/cm. If the desalting is stopped outside this range, the ink contains a large amount of impurities such as NaCl, and the storage stability of the ink is therefore poor.
JP2000345085, JP20003455095 disclose methods in which carbon black is ground in advance or hypochlorite is added while grinding to prepare hydrophilic carbon black.
JP2007002068, JP2007084597 disclose a method for preparing hydrophilic carbon black by liquid phase oxidation using hypochlorite solution. In this method, a dispersant is added, and the carbon black is pre-pulverized in water.
JP2008195837 discloses a method for obtaining carbon black having dispersion stability after oxidation treatment of the surface of carbon black with hypochlorite and then surface treatment with a hydrophilic organic surface treating agent, oxidation treatment alone or surface treatment with only hydrophilicity being not possible to achieve the above object.
JP2012102158 discloses a method for producing hydrophilic carbon black using hypochlorite, which requires addition of an alkali solution to control the pH of the reaction solution, and the pH of the reaction solution is maintained at 9.0 or more throughout the period from the start to the end of the oxidation step.
Hydrophilic carbon blacks prepared by liquid phase oxidation have been used in rubber applications such as carbon blacks oxidized by hydrogen peroxide solutions for butyl rubber, delayed scorch, reduced gas transmission (Nagornaya M.N., Razdyakonova G.I., Khodakova S.ya, The effect of functional groups of carbon black on rubber coatings [ J ]. Procedia Engineering 2016,152, 563-569); in US3330799, example 6 uses sodium hypochlorite to oxidize carbon black for 24 hours at room temperature, and the oxidized carbon black is added to butyl rubber for application to electrical insulation. US4075140 uses dilute nitric acid oxidized carbon black in rubber, which reduces the modulus of the rubber and increases the scorch time. US20190061424 uses hydrogen peroxide and/or ozone oxidized carbon black in heavy tires, slightly reducing the hysteresis properties of the rubber.
The technical solutions reported in the above documents have a common problem in that, in order to achieve a good oxidation effect, the oxidized carbon black needs to be subjected to desalting and purification treatment for many times. According to the invention, a large number of experiments are carried out to screen out proper carbon black and proper hypochlorite concentration, so that the consumption of hypochlorite is reduced as much as possible while the carbon black is ensured to be oxidized, and multiple desalting and purification treatments are avoided after the carbon black is oxidized.
The above documents report that the hydrophilic carbon black prepared by hypochlorite oxidation is rarely applied to rubber, and the oxidation degree of the used carbon black is low, so that the carbon black cannot be stably dispersed in water. The highly hydrophilic carbon black prepared by hypochlorite aqueous solution is used in rubber, so that the dispersion of the carbon black in the rubber can be improved, and the internal heat generation and the rolling resistance are effectively reduced.
Disclosure of Invention
The invention provides a method for preparing hydrophilic carbon black, which comprises the following steps:
(1) mixing furnace carbon black with a hypochlorite aqueous solution, and reacting to obtain a carbon black dispersion liquid;
(2) and (2) carrying out solid-liquid separation and drying on the carbon black dispersion liquid obtained in the step (1) to obtain hydrophilic carbon black.
In the process of the present invention, at least one aqueous hypochlorite solution is used to contact furnace carbon black particles in water and undergo liquid phase oxidation. The hypochlorite aqueous solution used in the present invention is not particularly limited, and is at least one selected from the group consisting of aqueous solutions of sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, lithium hypochlorite, barium hypochlorite, magnesium hypochlorite, ammonium hypochlorite, zinc hypochlorite, copper hypochlorite, and the like.
The pH value of the furnace carbon black is 7-10; preferably 8 to 9.
The DBP absorption of the furnace carbon black is 50 cm-180 cm3100g of; preferably 80-150 cm3/100g。
The nitrogen adsorption specific surface area of the furnace carbon black is 300m2The ratio of the total carbon content to the total carbon content is below g; preferably 100 to 300m2/g。
The average particle size of the furnace carbon black is 100-300 nm; preferably 200-300 nm.
The concentration of the hypochlorite aqueous solution is less than 1 mol/L; preferably 0.01 to 0.9 mol/L.
The carbon black concentration of the carbon black dispersion liquid is 30-200 g/L; preferably 50 to 100 g/L.
The reaction temperature is 30-100 ℃, and preferably 40-90 ℃. When the treatment temperature is lower than 30 ℃, hypochlorite hardly generates oxygen-containing functional groups on the surface of the carbon black, and when the treatment temperature is higher than 100 ℃, hypochlorite decomposition speed is accelerated.
The reaction time is 5 min-5 h, preferably 10 min-2 h.
The stirring is mechanical stirring or ultrasonic stirring, preferably mechanical stirring; the mechanical stirring speed is 50-500 rpm, preferably 50-400 rpm.
The solid-liquid separation is centrifugal separation or filtration separation, preferably centrifugal separation.
In the method of the present invention, the carbon black is subjected to liquid-phase oxidation treatment using hypochlorite to form an acid group on the surface, thereby obtaining hydrophilic carbon black.
The invention also discloses the hydrophilic carbon black obtained by the method.
The invention also discloses application of the hydrophilic carbon black in rubber.
The invention also discloses a preparation method of the rubber, which is characterized by comprising the following steps:
(1) mixing 70-40 parts by weight of hydrophilic carbon black with 30-60 parts by weight of raw rubber or latex, adding a rubber additive, and uniformly mixing to obtain a rubber compound;
(2) and (3) carrying out plate vulcanization on the rubber compound in the step (1) to obtain vulcanized rubber.
The raw rubber can be one or more of natural rubber, styrene butadiene rubber, butyl rubber and nitrile butadiene rubber; the latex can be one or more of natural latex, styrene-butadiene latex, butyronitrile latex and butyl latex.
The method disclosed by the invention has the advantages that the proper carbon black is selected, at least one hypochlorite aqueous solution is used, and the hypochlorite aqueous solution and the carbon black are subjected to liquid-phase oxidation reaction under the proper reaction condition, so that the oxidized carbon black has good hydrophilicity and can have excellent dispersion stability in water.
And under the appropriate condition, the hypochlorite with lower concentration is used, so that the waste of the oxidant is reduced under the condition of ensuring the dispersion stability of the carbon black in water, the cost is saved, and the subsequent purification and classification treatment of the hydrophilic carbon black can be effectively avoided. The hydrophilic carbon black is applied to the rubber, so that the breaking elongation of the rubber is improved, and the rolling resistance and the compression fatigue temperature rise are reduced.
The terms "above," "below," "greater than," "less than," and the like in this specification are intended to denote ranges of values which include the end point value itself.
The terms "comprising," "including," "containing," "having," and the like, as used herein, are not intended to exclude the inclusion of other elements or steps not listed in the present invention.
The carbon black has a DBP value (absorption of carbon black; oil-absorption of carbon black). Under the specified test conditions, 100g of carbon black absorbs dibutyl phthalate (DBP, di-n-butyl phthalate) in volume (cm)3) And (4) counting. To characterize the degree of aggregation of the carbon black. The DBP value allows calculation of the void volume between carbon black aggregates, which is a measure of the degree of aggregation and agglomeration of the carbon black. When carbon black is used as a rubber filler, the degree of aggregation of its particles affects the performance properties of the carbon black vulcanizate.
Drawings
1. FIG. 1 is a graph showing the change in storage modulus with strain of rubber 1 and rubber 1 (RPA-2000 rubber Analyzer, Taiwan high-speed railway testing Instrument Co., Ltd., NR-HCB denotes rubber 1 of example 1, and NR-CB denotes rubber 1 obtained in comparative example 1). FIG. 1 shows that rubber 1 has a low Δ G', indicating that hydrophilic carbon black HBC-1 has better dispersing properties in natural rubber.
2. FIG. 2 is a graph showing the loss factors of rubber 1 and rubber 1 as a function of strain (RPA-2000 rubber Analyzer, Taiwan high-speed railway testing Instrument Co., Ltd., NR-HCB denotes rubber 1 obtained in example 1, and NR-CB denotes rubber 1 obtained in comparative example 1). FIG. 2 shows that the loss factor of rubber 1 is lower than that of rubber 1, indicating that the hydrophilic carbon black HBC-1 has a lower rolling resistance in natural rubber.
Examples
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
Example 1
Commercially available furnace carbon black (DBP absorption 150 cm)3100g, nitrogen adsorption specific surface area of 240m2And/g) 300g of the carbon black is added into 3L of 0.89mol/L sodium hypochlorite solution, and the mixture is subjected to ultrasonic vibration in an ultrasonic cleaner (KH7200 type), so that the carbon black is uniformly dispersed in the sodium hypochlorite solution, the temperature is controlled to be 60 ℃, and the reaction is carried out for 3 hours under continuous heat preservation and stirring.
And (3) after the liquid-phase oxidation reaction is finished, dehydrating the carbon black solution in a centrifugal machine, controlling the rotating speed of the centrifugal machine to be 9000rpm, and separating the hydrophilic carbon black from the aqueous solution. And drying to obtain the hydrophilic carbon black HCB-1.
The obtained hydrophilic carbon black is mixed according to a formula (100 parts by weight of natural rubber, 50 parts by weight of hydrophilic carbon black HCB-1, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of anti-aging agent 4010NA, 1.2 parts by weight of accelerator CZ and 2 parts by weight of sulfur) to obtain a rubber compound. And vulcanizing the mixed rubber at 145 ℃ for positive vulcanization time to obtain hydrophilic carbon black/natural rubber vulcanized rubber which is marked as rubber 1.
Example 2
Commercially available furnace carbon black (DBP absorption of 130 cm)3100g, nitrogen adsorption specific surface area of 210m2Per gram) 200g of the solution was added to 3L of 0.54mol/L potassium hypochlorite solution and stirred at 200rpm to uniformly disperse the carbon black in the potassium hypochlorite solution, the temperature was controlled at 60 ℃ and the reaction was continued with stirring for 2 hours with constant temperature.
And (3) after the liquid-phase oxidation reaction is finished, dehydrating the carbon black solution in a centrifugal machine, controlling the rotating speed of the centrifugal machine to be 9000rpm, and separating the hydrophilic carbon black from the aqueous solution. And drying to obtain the hydrophilic carbon black HCB-2.
The obtained hydrophilic carbon black is mixed according to a formula (100 parts by weight of styrene butadiene rubber, 50 parts by weight of hydrophilic carbon black HCB-2, 3 parts by weight of zinc oxide, 1 part by weight of stearic acid, 1.34 parts by weight of accelerator NS and 1.2 parts by weight of sulfur) to obtain a rubber compound. And vulcanizing the mixed rubber at 151 ℃ for normal vulcanization time to obtain hydrophilic carbon black/styrene butadiene rubber vulcanized rubber, which is marked as rubber 2.
Example 3
Commercially available furnace carbon black (DBP absorption 120 cm)3100g, nitrogen adsorption specific surface area of 190m2Per gram) 150g of the carbon black is added into 3L of 0.68mol/L sodium hypochlorite solution and stirred at the rotating speed of 300rpm, so that the carbon black is uniformly dispersed in the sodium hypochlorite solution, the temperature is controlled to be 80 ℃, and the reaction is carried out for 1 hour by continuous heat preservation and stirring.
And (3) after the liquid-phase oxidation reaction is finished, dehydrating the carbon black solution in a centrifugal machine, controlling the rotating speed of the centrifugal machine to be 7000rpm, and separating the hydrophilic carbon black from the aqueous solution. And drying to obtain the hydrophilic carbon black HCB-3.
The obtained hydrophilic carbon black was mixed according to the formulation (100 parts by weight of butyl rubber, 50 parts by weight of hydrophilic carbon black HCB-3, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 2 parts by weight of antioxidant 4010NA, 1.5 parts by weight of accelerator CZ, 0.2 parts by weight of accelerator M, 2.5 parts by weight of sulfur) to obtain a rubber compound. And vulcanizing the rubber compound at 160 ℃ for positive vulcanization time to obtain hydrophilic carbon black/butyl rubber vulcanized rubber, which is marked as rubber 3.
Example 4
Commercially available furnace carbon black (DBP absorption of 146 cm)3100g, nitrogen adsorption specific surface area of 230m2Per gram) 200g of the carbon black was added to 3.5L of 0.89mol/L potassium hypochlorite solution and stirred at 240rpm to uniformly disperse the carbon black in the potassium hypochlorite solution, the temperature was controlled at 70 ℃ and the reaction was continued with stirring for 0.5 hour under constant temperature.
And (3) after the liquid-phase oxidation reaction is finished, dehydrating the carbon black solution in a centrifugal machine, controlling the rotating speed of the centrifugal machine to be 8000rpm, and separating the hydrophilic carbon black from the water solution. And drying to obtain the hydrophilic carbon black HCB-4.
Mixing the obtained hydrophilic carbon black according to a formula (100 parts by weight of styrene-butadiene latex, 50 parts by weight of hydrophilic carbon black HCB-4, 3 parts by weight of zinc oxide and 1 part by weight of stearic acid), drying in an oven at 80 ℃ for 24 hours, and then sequentially adding 1.34 parts by weight of accelerator NS and 1.2 parts by weight of sulfur, and uniformly mixing to obtain the rubber compound. And vulcanizing the mixed rubber at 151 ℃ for normal vulcanization time to obtain hydrophilic carbon black/styrene butadiene rubber vulcanized rubber which is marked as rubber 4.
Example 5
Commercially available furnace carbon black (DBP absorption of 125 cm)3100g, nitrogen adsorption specific surface area 253m2And/g) 200g of the carbon black is added into 3L of 0.54mol/L sodium hypochlorite solution and stirred at the rotating speed of 240rpm, so that the carbon black is uniformly dispersed in the sodium hypochlorite solution, the temperature is controlled to be 60 ℃, and the reaction is continuously kept for 4 hours under stirring.
And (3) after the liquid-phase oxidation reaction is finished, dehydrating the carbon black solution in a centrifugal machine, controlling the rotating speed of the centrifugal machine to be 7000rpm, and separating the hydrophilic carbon black from the aqueous solution. And drying to obtain the hydrophilic carbon black HCB-5.
The obtained hydrophilic carbon black is mixed according to a formula (100 parts by weight of natural rubber, 50 parts by weight of hydrophilic carbon black HCB-5, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of anti-aging agent 4010NA, 1.2 parts by weight of accelerator CZ and 2 parts by weight of sulfur) to obtain a rubber compound. And vulcanizing the mixed rubber at 145 ℃ for positive vulcanization time to obtain hydrophilic carbon black/natural rubber vulcanized rubber, which is marked as rubber 5.
Example 6
Commercially available furnace carbon black (DBP absorption 120 cm)3100g, nitrogen adsorption specific surface area of 260m2Per gram) 300 grams of the solution was added to 3.5 liters of 0.54 mol/liter potassium hypochlorite solution and stirred at 240rpm to uniformly disperse the carbon black in the potassium hypochlorite solution, the temperature was controlled at 60 ℃, and the reaction was stirred with continuous heat preservationFor 1 hour.
And (3) after the liquid-phase oxidation reaction is finished, dehydrating the carbon black solution in a centrifugal machine, controlling the rotating speed of the centrifugal machine to be 8000rpm, and separating the hydrophilic carbon black from the water solution. And drying to obtain the hydrophilic carbon black HCB-6.
The obtained hydrophilic carbon black is mixed according to a formula (100 parts by weight of natural rubber, 50 parts by weight of hydrophilic carbon black HCB-6, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of anti-aging agent 4010NA, 1.2 parts by weight of accelerator CZ and 2 parts by weight of sulfur) to obtain a rubber compound. And vulcanizing the mixed rubber at 145 ℃ for positive vulcanization time to obtain hydrophilic carbon black/natural rubber vulcanized rubber, which is marked as rubber 6.
Comparative example 1
Commercially available furnace carbon black (DBP absorption 150 cm)3100g, nitrogen adsorption specific surface area of 240m2Per g) according to the formula (100 parts by weight of natural rubber, 50 parts by weight of furnace carbon black, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of anti-aging agent 4010NA, 1.2 parts by weight of accelerator CZ, 2 parts by weight of sulfur) to obtain the rubber compound. The rubber mix was vulcanized at 145 ℃ for a positive cure time to give a commercial furnace black/natural rubber vulcanizate designated as rubber 1.
Comparative example 2
Commercially available furnace carbon black (DBP absorption of 130 cm)3100g, nitrogen adsorption specific surface area of 210m2And/g) mixing according to a formula (100 parts by weight of styrene-butadiene rubber, 50 parts by weight of furnace carbon black, 3 parts by weight of zinc oxide, 1 part by weight of stearic acid, 1.34 parts by weight of accelerator NS and 1.2 parts by weight of sulfur) to obtain a rubber compound. And vulcanizing the mixed rubber at 151 ℃ for positive vulcanization time to obtain the commercial furnace carbon black/styrene butadiene rubber vulcanized rubber which is marked as rubber 2.
Comparative example 3
Commercially available furnace carbon black (DBP absorption 120 cm)3100g, nitrogen adsorption specific surface area of 190m2Per g) according to the formulation (100 parts by weight of butyl rubber, 50 parts by weight of furnace black, 3 parts by weight of zinc oxide, 1 part by weight of stearic acid, 1.34 parts by weightAccelerator NS in a certain amount, and sulfur in 1.2 weight parts) to obtain the rubber compound. The rubber compound was vulcanized at 160 ℃ for a positive vulcanization time to give a commercial furnace black/butyl rubber vulcanizate, designated as rubber 3.
The hydrophilic carbon black obtained in examples 1 to 6, after drying, had a soft surface, and no white crystals were precipitated on the wall of the beaker, and could be used directly without purification and classification post-treatment.
Sedimentation stability analysis of hydrophilic carbon Black
And (3) carrying out sedimentation stability analysis on the obtained hydrophilic carbon black, adding a certain amount of unoxidized furnace carbon black and hydrophilic carbon black into water respectively, shaking up, and observing the change condition of the carbon black solution. Observation shows that after the sample is stood for 7 days, the unoxidized furnace carbon black solution is completely layered, and the upper layer solution is completely transparent; the hydrophilic carbon black solution is uniform and has no delamination phenomenon.
Table 1 shows the particle size and potential of unoxidized furnace blacks and carbon blacks from examples 1-6 (test equipment: nanometer laser particle size potential Analyzer ZETASIZER/Nano ZS90, Malvern, UK).
TABLE 1 particle size and potential of unoxidized furnace blacks and hydrophilic blacks obtained in examples 1-6
Note: CB represents a commercially available furnace carbon black
HCB represents hydrophilic carbon black
Conclusion
The granularity of the carbon black after oxidation is reduced, and the potential value of the carbon black solution is changed from a positive value to a negative value, which shows that the dispersion stability of the carbon black in water is greatly improved.
XPS elemental analysis of carbon black
Table 2 shows XPS elemental analysis (test equipment: X-ray photoelectron spectrometer ESCALB 250, ThermoFisher Scientific Co., U.S.A.) of carbon blacks from examples 1-6.
TABLE 2 carbon Black element analysis of hydrophilic carbon blacks obtained in inventive examples 1-6
Note: CB represents a commercially available furnace carbon black
HCB represents hydrophilic carbon black
C% and O% are mass percentages.
Conclusion
The oxygen content of the oxidized carbon black is increased rapidly, which shows that the oxygen-containing functional groups on the surface of the carbon black are increased, and the hydrophilic acid functional groups are increased. Therefore, the water solubility of the carbon black after hypochlorite oxidation is greatly improved.
Performance testing of rubber
Table 3 shows the comparison of the properties of the rubbers obtained in examples 1 to 6 with those obtained in comparative examples 1 to 3 (scorch time: MR-C3 rotor-less vulcanizer, Beijing Ruidayuchen instruments Ltd.; elongation at break: tensile testing machine AI-7000S, Taiwan high-speed rail testing instruments Ltd., compression fatigue temperature rise: rubber compression heat generation testing machine RH-2000N, Taiwan high-speed rail testing instruments Ltd., hardness: Shore durometer, Shanghai Sichuan land measuring instruments Ltd.).
TABLE 3 comparison of the properties of the rubbers obtained in examples 1 to 6 with those of comparative examples 1 to 3
Conclusion
After hydrophilic carbon black is added to rubber, the scorch time is reduced, but the elongation at break is improved and the compression fatigue temperature rise is reduced.
Comparison of RPA tests of rubber 1 and rubber 1
Conclusion
By comparing FIGS. 1 and 2(RPA-2000 rubber Analyzer, Taiwan high-speed railway testing Instrument Co., Ltd., NR-HCB denotes rubber 1 of example 1, and NR-CB denotes rubber 1 obtained in comparative example 1), it can be seen that rubber 1 has a lower Δ G' than rubber 1, indicating that hydrophilic carbon black HBC-1 has a better dispersion property in natural rubber. The loss factor of rubber 1 was lower than that of rubber 1, indicating that the hydrophilic carbon black HBC-1 has a lower rolling resistance in natural rubber.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911407274.1A CN111171607B (en) | 2020-04-09 | 2020-04-09 | A kind of method for preparing hydrophilic carbon black, hydrophilic carbon black and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911407274.1A CN111171607B (en) | 2020-04-09 | 2020-04-09 | A kind of method for preparing hydrophilic carbon black, hydrophilic carbon black and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111171607A CN111171607A (en) | 2020-05-19 |
| CN111171607B true CN111171607B (en) | 2021-05-04 |
Family
ID=70654281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911407274.1A Active CN111171607B (en) | 2020-04-09 | 2020-04-09 | A kind of method for preparing hydrophilic carbon black, hydrophilic carbon black and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111171607B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111471216A (en) * | 2020-03-30 | 2020-07-31 | 青岛黑猫新材料研究院有限公司 | Modified thermal cracking carbon black |
| CN111471220A (en) * | 2020-03-30 | 2020-07-31 | 青岛黑猫新材料研究院有限公司 | Rubber composition |
| CN111484649A (en) * | 2020-03-30 | 2020-08-04 | 青岛黑猫新材料研究院有限公司 | Preparation method of modified thermal cracking carbon black |
| CN114574001B (en) * | 2020-11-30 | 2023-04-28 | 北京化工大学 | Method for preparing hydrophilic carbon black through biomimetic modification of phenolic amine and hydrophilic carbon black |
| CN113429809A (en) * | 2021-05-31 | 2021-09-24 | 安徽德瑞新材料科技有限公司 | Processing technology of carbon black for ultrablue phase color matching |
| CN113307523A (en) * | 2021-06-01 | 2021-08-27 | 安徽德瑞新材料科技有限公司 | Method for preparing water-soluble carbon black, water-soluble carbon black and application thereof |
| CN114213902B (en) * | 2021-12-14 | 2023-03-10 | 湖南金阳烯碳新材料股份有限公司 | Water-based graphene conductive ink for battery and preparation method and application thereof |
| CN116041987B (en) * | 2022-12-12 | 2024-12-24 | 上海色如丹数码科技股份有限公司 | Preparation method of self-dispersing water-based carbon black |
| CN116041986B (en) * | 2022-12-22 | 2024-06-28 | 山西盛达威科技有限公司 | A method for preparing water-soluble carbon black |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3330799A (en) * | 1966-01-24 | 1967-07-11 | Huber Corp J M | Electrically insulating vulcanizates containing oxidized carbon black |
| JPH10120958A (en) * | 1996-08-26 | 1998-05-12 | Orient Chem Ind Ltd | Aqueous pigment ink composition and its production |
| TW200521194A (en) * | 2003-07-16 | 2005-07-01 | Lexmark Int Inc | Pigmented inkjet ink |
| CN101824126A (en) * | 2010-05-07 | 2010-09-08 | 华东理工大学 | Hydrophilic carbon black |
| CN103031757A (en) * | 2012-12-28 | 2013-04-10 | 苏州世名科技股份有限公司 | Black water-based color paste for acrylic stock solution coloring and preparation method of black water-based color paste |
| CN109368657A (en) * | 2018-08-22 | 2019-02-22 | 中国矿业大学 | Preparation method of framework metal highly dispersed hierarchical porous H-ZSM-5 molecular sieve |
| CN110105793A (en) * | 2019-06-19 | 2019-08-09 | 焦作市和兴化学工业有限公司 | A kind of method of acetylene carbon black modification |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7066434B2 (en) * | 2017-03-10 | 2022-05-13 | キヤノン株式会社 | Water-based inks, ink cartridges, and inkjet recording methods |
-
2020
- 2020-04-09 CN CN201911407274.1A patent/CN111171607B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3330799A (en) * | 1966-01-24 | 1967-07-11 | Huber Corp J M | Electrically insulating vulcanizates containing oxidized carbon black |
| JPH10120958A (en) * | 1996-08-26 | 1998-05-12 | Orient Chem Ind Ltd | Aqueous pigment ink composition and its production |
| TW200521194A (en) * | 2003-07-16 | 2005-07-01 | Lexmark Int Inc | Pigmented inkjet ink |
| CN101824126A (en) * | 2010-05-07 | 2010-09-08 | 华东理工大学 | Hydrophilic carbon black |
| CN103031757A (en) * | 2012-12-28 | 2013-04-10 | 苏州世名科技股份有限公司 | Black water-based color paste for acrylic stock solution coloring and preparation method of black water-based color paste |
| CN109368657A (en) * | 2018-08-22 | 2019-02-22 | 中国矿业大学 | Preparation method of framework metal highly dispersed hierarchical porous H-ZSM-5 molecular sieve |
| CN110105793A (en) * | 2019-06-19 | 2019-08-09 | 焦作市和兴化学工业有限公司 | A kind of method of acetylene carbon black modification |
Non-Patent Citations (4)
| Title |
|---|
| "Improving the electrochemical behavior of carbon black and carbon filaments by oxidation";C.AFrysz 等;《Carbon》;19971231;第35卷(第8期);112-117 * |
| "Synthesis of uniform mesoporous ZSM-5 using hydrophilic carbon as a hard template";Han, Shunyu 等;《MATERIALS CHEMISTRY AND PHYSICS》;20160701;第177卷;1111-1127 * |
| "不同粒径炭黑填充天然橡胶黏超弹性能表征及其减振特性";袁子豪;《中国优秀硕士学位论文全文数据库（工程科技I辑）》;20190215(第2期);B016-411 * |
| "水性炭黑色浆的制备及性能研究";林丽隽;《中国优秀硕士学位论文全文数据库（工程科技I辑）》;20130515(第5期);B015-96 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111171607A (en) | 2020-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111171607B (en) | A kind of method for preparing hydrophilic carbon black, hydrophilic carbon black and application thereof | |
| US6130283A (en) | Aluminum hydroxide, method for producing the same, and method of use of the same | |
| KR102762109B1 (en) | Silica-graphene-based carbon composite particles and elastomeric materials containing such particles | |
| CN103254400A (en) | Preparation method of graphene oxide/waterborne polyurethane nanometer composite material | |
| TW201237082A (en) | Improved elastomer formulations | |
| Yu et al. | Polyrhodanine mediated interface in natural rubber/carbon black composites toward ultralow energy loss | |
| WO2013080843A1 (en) | Functional-group-modified carbon material, and method for producing same | |
| CN102108144A (en) | Preparation method of epoxidized natural rubber masterbatch with highly dispersed nano-silicon dioxide/carbon black | |
| CN103819760A (en) | Process method for preparing high-performance carbon black masterbatch | |
| CN110105793A (en) | A kind of method of acetylene carbon black modification | |
| US12116485B2 (en) | Surface modified carbon black to simultaneously improve rolling resistance, wet traction, and wear resistance | |
| JP6869592B2 (en) | Inorganic composite for rubber reinforcement, manufacturing method thereof, and rubber composition for tires containing the same. | |
| JP7295520B2 (en) | Rubber composition for tires | |
| JP3633201B2 (en) | Aluminum hydroxide, process for producing the same and rubber composition for tire tread using the same | |
| Song et al. | Tribological properties of α-, and β-manganese dioxide/polytetrafluoroethylene composites under the dry sliding condition | |
| RU2358991C2 (en) | Powdered white composition of vulcanisation promoter and rubber composition | |
| CN112778584A (en) | Rubber composite master batch and preparation method thereof | |
| CN114524978B (en) | Chitosan/silicon dioxide nano hybrid material and biomimetic mineralization preparation method and application thereof | |
| JP5403213B2 (en) | Surface-treated magnetic iron oxide particle powder, and black paint and rubber / resin composition using the surface-treated magnetic iron oxide particle powder | |
| JPS61255946A (en) | Improved rubber composition | |
| CN108017874A (en) | A kind of graphene/hard nanometer particle cooperative phenol-formaldehyde resin modified wear-resistant material | |
| CN109306094B (en) | Preparation method of graphene rubber masterbatch | |
| CN111423641B (en) | A kind of method for preparing highly dispersed carbon black/rubber nanocomposite | |
| CN108192139B (en) | Modification method of carbon nano tube used as rubber filler | |
| Chen et al. | Fabrication and properties of superparamagnetic UV-curable nanocomposites based on covalently linked waterborne polyurethane/functionalized hollow Ni 0.3 Zn 0.5 Fe 2 O 4 microspheres |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |