CN118103460A - Carbon black and method for producing carbon black - Google Patents
Carbon black and method for producing carbon black Download PDFInfo
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- CN118103460A CN118103460A CN202280007369.8A CN202280007369A CN118103460A CN 118103460 A CN118103460 A CN 118103460A CN 202280007369 A CN202280007369 A CN 202280007369A CN 118103460 A CN118103460 A CN 118103460A
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- 239000006229 carbon black Substances 0.000 title claims abstract description 165
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 229920001971 elastomer Polymers 0.000 claims abstract description 83
- 239000005060 rubber Substances 0.000 claims abstract description 83
- 238000001179 sorption measurement Methods 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010521 absorption reaction Methods 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 7
- 239000011630 iodine Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims description 43
- 230000002378 acidificating effect Effects 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229920000800 acrylic rubber Polymers 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000010292 electrical insulation Methods 0.000 abstract description 15
- 239000002253 acid Substances 0.000 abstract description 10
- 235000019241 carbon black Nutrition 0.000 description 150
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 27
- 238000000034 method Methods 0.000 description 27
- 239000003921 oil Substances 0.000 description 17
- 239000000446 fuel Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 238000002485 combustion reaction Methods 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 10
- -1 alkali metal salt Chemical class 0.000 description 9
- 238000005469 granulation Methods 0.000 description 9
- 230000003179 granulation Effects 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000012266 salt solution Substances 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000567 combustion gas Substances 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 238000005550 wet granulation Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000110 cooling liquid Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WHRZCXAVMTUTDD-UHFFFAOYSA-N 1h-furo[2,3-d]pyrimidin-2-one Chemical compound N1C(=O)N=C2OC=CC2=C1 WHRZCXAVMTUTDD-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000006173 Larrea tridentata Nutrition 0.000 description 1
- 244000073231 Larrea tridentata Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229960002126 creosote Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
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
-
- 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
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application provides a carbon black for further improving electrical insulation and mechanical strength of rubber and a method for producing the same. The concentration of the strong acid group in the carbon black is 0.50X10 ‑5 mol/g or less, the iodine adsorption amount (IA) is 50 to 70mg/g, the ratio of the nitrogen adsorption specific surface area (N 2 SA) to the IA (N 2 SA/IA) is 1.20X10 3～1.50×103m2/g, and the DBP absorption amount is 130 to 150cm 3/100 g.
Description
Technical Field
The present invention relates to a carbon black and a method for producing the same.
Background
Carbon black is used for a variety of purposes. For example, carbon black is added as a filler of rubber to increase the mechanical strength of the rubber part. The rubber to which the carbon black is added is also various in use.
The properties required of carbon black to be added to rubber are various depending on the application. For example, rubber components (e.g., radiator hoses, etc.) for automobiles are sometimes configured to contact metal components. In addition to mechanical strength, such rubber members require high electrical insulation to prevent the metal members from being electrically corroded due to a potential difference between the metal members in contact therewith. However, since carbon black itself has conductivity, the addition of carbon black may deteriorate the electrical insulation of rubber parts. In this case, there is a need for a carbon black which does not deteriorate electrical insulation even when added to a rubber member.
In response to the above-mentioned demand, patent document 1 (japanese patent application laid-open No. 2003-306813) discloses a technique for achieving both high resistance and reinforcement in a radiator hose or the like. For this reason, patent document 1 describes that the specific nitrogen adsorption surface area (N 2 SA), the DBP absorption (DBP), the ratio of N 2 SA to the iodine adsorption, the toluene coloring transmittance, the F value, and the hydrogen content in carbon black are set to specific values, respectively.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2003-306813.
Disclosure of Invention
Problems to be solved by the invention
In recent years, there has been an increasing demand for carbon black which does not deteriorate electrical insulation even when added to rubber parts, due to the demands of automobile development for pure electric power and for prolonging the life of parts. Specifically, since the structure of the automobile is composed of a plurality of different metals, the potential difference between the metal members in contact with the rubber member increases. That is, a rubber member is required to have higher electrical insulation than conventional ones.
However, among rubbers used for rubber parts, polar rubbers are widely used as rubber parts for automobiles such as radiator hoses from the viewpoints of heat resistance, oil resistance and weather resistance. It is known that such polar rubbers, due to their molecular structure, have difficulty in well dispersing carbon black having surface functional groups. In addition, in general, when carbon black is added as a filler, it is difficult to obtain a satisfactory effect of adding the filler if good dispersibility of the filler is not ensured.
Therefore, for rubber parts using polar rubber in which it is difficult to satisfactorily disperse the filler, carbon black, which can impart mechanical strength without impairing electrical insulation against a potential difference larger than before, is required as the filler.
In view of the above, an object of the present invention is to provide a carbon black and a method for producing the same, which can realize good electrical insulation and mechanical strength when combined with a rubber member.
Means for solving the problems
The inventors of the present invention have found that the above problems can be solved by limiting the iodine adsorption amount, the nitrogen adsorption specific surface area to IA ratio (N 2 SA/IA), the DBP adsorption amount, and the strong acid group concentration of carbon black to specific ranges, respectively.
That is, the present invention includes the following matters.
[1] A carbon black having a strong acid group concentration of 0.50X10 -5 mol/g or less, an iodine adsorption amount (IA) of 50 to 70mg/g, a nitrogen adsorption specific surface area (N 2 SA) to IA ratio (N 2 SA/IA) of 1.20X10 3～1.50×103m2/g and a DBP adsorption amount of 130 to 150cm 3/100 g.
[2] The carbon black of [1], wherein the carbon black is added as a filler to a polar rubber component.
[3] The carbon black of [2], wherein the polar rubber member is a material configured to be in contact with a metal.
[4] The carbon black of [2] or [3], wherein the polar rubber member comprises an acrylic rubber.
[5] The carbon black according to any one of [2] to [4], wherein the carbon black is added in an amount of 30 to 90 parts by mass to 100 parts by mass of the rubber component in the polar rubber member.
[6] The carbon black of any one of [2] to [5], wherein the polar rubber component is an automobile component.
[7] A method of making carbon black comprising: a step of incompletely combusting the hydrocarbon raw material to produce a carbon black raw material; and heating the carbon black raw material at 300 to 400 ℃ in an inert gas atmosphere.
Effects of the invention
The carbon black and the method for producing the same can provide good electrical insulation and mechanical strength of rubber when being matched with a rubber component.
Drawings
Fig. 1 is a block diagram showing a process sequence for producing carbon black according to an embodiment of the present invention.
FIG. 2 is a schematic view showing the structure of a reaction furnace.
Fig. 3 is a graph showing the relationship between tensile strength and volume resistivity.
Detailed Description
An embodiment of the present invention will be described below.
The carbon black of the present embodiment is added to a rubber member and is a filler for improving the mechanical strength of the rubber member.
The carbon black of the present embodiment has the following matters.
(A) The concentration of the strongly acidic group is 0.50X10 -5 mol/g or less,
(B) The iodine adsorption amount (hereinafter referred to as IA) is 50 to 70mg/g;
(C) The ratio of nitrogen adsorption specific surface area (hereinafter referred to as N 2 SA) to IA (N 2 SA/IA) was 1.20X10- 3～1.50×103m2/g,
(D) The DBP absorption is 130-150 cm 3/100 g.
The carbon black of the present embodiment has the above-described characteristics, and therefore, when added as a filler to a rubber member, imparts high mechanical strength while maintaining the flexibility of the rubber member, and maintains high resistivity.
The rubber member to which the carbon black of the present embodiment is added preferably includes a polar rubber.
The polar rubber is not particularly limited, and examples thereof include acrylic rubber, nitrile rubber, chloroprene rubber, chlorosulfonated polyethylene rubber, urethane rubber, epichlorohydrin rubber, and the like. Preferably, the polar rubber comprises an acrylic rubber.
From the viewpoint of improving the mechanical strength of the rubber member, the carbon black of the present embodiment is preferably added in an amount of 30 to 90 parts by mass to 100 parts by mass of the rubber component, and from the viewpoint of maintaining the electrical insulation of the rubber member, the carbon black of the present embodiment is preferably added in a proportion of 45 to 75 parts by mass.
Next, specific matters of the carbon black to be transmitted in the present embodiment will be described in detail.
(A) Strong acid group concentration: 0.50X10 -5 mol/g or less
The strong acid group concentration is a value of the amount of strong acid groups (mainly carboxyl groups) present on the surface of carbon black expressed in terms of the amount of substance per unit mass of carbon black (10 -5 mol/g). When the value of the concentration of the strongly acidic group is large, the wettability of the carbon black with respect to the rubber, particularly with respect to the polar rubber, is reduced, and as a result, the dispersibility of the carbon black in the polar rubber is reduced.
The concentration of the strongly acidic group in the carbon black of this embodiment is limited to 0.50X10 -5 mol/g or less.
When the concentration of the strongly acidic group is 0.50X10 -5 mol/g or less, the dispersibility of the carbon black in the polar rubber is improved. As a result, the physical and chemical interactions between the carbon black surface and the polar rubber molecular chains are increased, and the mechanical strength of the rubber component including the polar rubber can be further improved.
In addition, since the dispersibility of carbon black in polar rubber is improved, contact between conductive carbon black particles becomes difficult. As a result, electrical insulation of the rubber member including the polar rubber is easily maintained.
The concentration of the strongly acidic group can be determined by the following method.
A carbon black sample (5 g) was precisely weighed and pulverized, 50mL of a sodium bicarbonate solution (0.1 mol/L) was added thereto, and the mixture was shaken at room temperature for 4 hours to neutralize the strongly acidic functional groups on the surface of the carbon black. Thereafter, in order to obtain the amount of remaining sodium bicarbonate not used for neutralization, 20mL of supernatant after centrifugation of carbon black was titrated with 0.025mol/L sulfuric acid, and a blank test (titration of 20mL of stock solution of 0.1mol/L sodium bicarbonate not used in the above reaction with 0.025mol/L sulfuric acid) was performed simultaneously, and the amount of strongly acidic functional groups per unit mass (10 -5 mol/g) was calculated from the difference between the two.
For example, according to the above measurement method, when the empty drop amount is 39.27ml and the supernatant drop amount after the neutralization reaction is 39.25ml, the difference between the two is 0.02ml, and therefore, the strongly acidic group concentration can be calculated to be 0.2X10 -5 mol/g.
(B)IA：50～70mg/g
IA is a value of specific surface area of carbon black expressed as an adsorption amount of iodine molecule per unit mass of carbon black in a liquid phase (mg/g). By limiting the IA to 50mg/g or more, a rubber member can be given sufficient mechanical strength. Further, IA is 70mg/g or less, so that high electrical insulation can be maintained when a rubber member is added.
(C)N2SA/IA：1.20×103～1.50×103m2/g
N 2 SA is a value of the specific surface area of carbon black expressed by the molecular adsorption amount of nitrogen per unit mass of carbon black (m 2/g). Similar to IA, although N 2 SA represents the specific surface area of carbon black, IA is also a value depending on the amount of surface functional groups of carbon black (the larger the amount of acidic functional groups, the more difficult iodine molecules are to be adsorbed, and IA has a slightly lower value than N 2 SA). In addition, N 2 SA can be used in the following manner according to JIS K6217-7:2013 "test method of basic carbon black performance for rubber" (refer to ASTM D6556-16).
The value of N 2 SA divided by the value of IA is an index indicating the surface activity of carbon black. The value of N 2 SA/IA is calculated by setting the unit of the value of N 2 SA as m 2/g and the unit of IA as mg/g. The larger the value of N 2 SA/IA, the more the surface functional group content of the carbon black. When the surface functional group amount of the carbon black is large, the surface of the carbon black is easily chemically reacted through the surface functional group. That is, the value of the surface activity of carbon black refers to a quantitative representation of how easily a chemical reaction of the carbon black surface occurs.
According to the findings of the present inventors, in order to achieve both the degree of adsorption of polar rubber molecules and the degree of difficulty in aggregation between carbon blacks, it is necessary to not only make the value of the strong acid group concentration of carbon black smaller than a predetermined value, but also make the surface functional group amount of carbon black fall within a predetermined range. That is, the value of the concentration of the strongly acidic group and the value of N 2 SA/IA need to be considered. From the viewpoint of maintaining high electrical insulation, it is preferable to limit the value of the concentration of the strongly acidic group to 0.50X10 -5 mol/g or less and to limit the value of N 2 SA/IA to 1.20X10 3m2/g or more.
In addition, from the viewpoint of production of carbon black, specifically, from the viewpoint of difficulty in remaining unburned oil or easiness in granulation, the value of N 2 SA/IA is preferably 1.50X10 3m2/g or less.
(D) DBP absorption=130 to 150cm 3/100 g
The DBP absorption is a value of the carbon black structure expressed as the absorption of DBP (dibutyl phthalate) to 100g of carbon black (cm 3/100 g). The porosity between carbon black polymers is positively correlated to the carbon black structure. Therefore, the larger the DBP absorption value, the more developed the carbon black structure, and the more easily adsorption or proximity/contact between particles occurs. The DBP absorption is preferably 130cm 3/100 g or more from the viewpoint of good adsorption of carbon black to rubber molecules and imparting high mechanical strength to rubber parts. In addition, from the viewpoint of preventing the approaching/contacting between carbon black particles and maintaining the high electrical insulation of the rubber member, the DBP absorption is preferably 150cm 3/100 g or less.
(E) Other specific matters
The carbon black preferably has a specific tinting strength Tint (%) of 85 to 115. The specific tinting strength Tint (%) is related to the size of the particle diameter, the degree of structural development, and the size distribution of the polymer, and the smaller the particle diameter, the lower the degree of structural development, and the sharper the size distribution of the polymer (i.e., the uniform size of the polymer), the higher the displayed value. Therefore, from the viewpoint of uniform distribution in rubber molecules and improvement of rubber reinforcing property, the specific tinting strength Tint (%) is preferably 85 or more. In addition, from the viewpoints of not increasing the complex viscosity of the rubber and good rubber processability, the value of the specific tinting strength Tint (%) is preferably 115 or less. Wherein, the specific tinting strength Tint (%) can be determined by JIS K6217-5:2010 "test method of carbon black basic properties for rubber" was obtained by the method described in "test method of carbon black basic properties for rubber".
The carbon black preferably has a 24M4DBP absorption (cm 3/100 g) of 90 to 115. The 24M4DBP absorption (cm 3/100 g) represents the amount of the structure having strong bonding strength between particles that is not damaged even by strong pressure after compression 4 times at 24000 lbs/(inch) 2 in the carbon black structure. The larger the 24M4DBP value, the easier it is to form a skeletal carbon black network in the rubber. From the viewpoint of forming a large amount of carbon black network and imparting sufficient reinforcing property to rubber, the value of 24M4DBP absorption is preferably 90 or more. In addition, from the viewpoints of not increasing the complex viscosity of the rubber and good rubber processability, the 24M4DBP absorption value is preferably 115 or less. The 24M4DBP absorption amount can be determined by JIS K6217-4:2017, "test method of carbon black basic Performance for rubber" was obtained by the method described in "test method of carbon black basic Performance for rubber".
Method for producing carbon black according to this embodiment
The carbon black of the present embodiment can be obtained by appropriately adjusting the reaction conditions in a general method for producing carbon black such as an oil furnace method. An example of the method for producing carbon black according to the present embodiment will be described below.
Fig. 1 is a block diagram showing a process sequence for producing carbon black according to an embodiment of the present invention. FIG. 2 is a schematic view of an example of a reaction furnace. As shown in fig. 1, the carbon black of one embodiment of the present invention can be produced by sequentially performing a reaction process S1, a granulation process S2, a drying process S3, and a heating process S4. First, in the reaction step S1, a carbon black raw material is produced in the reaction furnace 10.
The reactor 10 has a cylindrical shape and includes a fuel combustion zone 4, a raw material introduction zone 6, and a reaction zone 8.
The fuel combustion zone 4 is a portion that generates high-temperature combustion gas. The fuel combustion zone 4 is provided with an oxygen-containing gas introduction port 1, a burner 2, and an alkali metal salt/aqueous solution supply nozzle 3. An oxygen-containing gas (oxygen, air, etc.) is introduced into the fuel combustion zone 4 from the oxygen-containing gas introduction port 1. In addition, fuel (FCC resid, hydrogen, carbon monoxide, natural gas, petroleum gas, etc.) is supplied from the burner 2 to the fuel combustion zone 4. Thereby, high-temperature combustion gas is generated. Sodium, potassium carbonate, chloride, hydroxide, etc. as an alkali metal salt/aqueous solution, are supplied from the alkali metal salt/aqueous solution supply nozzle 3 to the fuel combustion zone 4. By adding an alkali metal salt/aqueous solution, the carbon black structure can be adjusted to be underdeveloped in the raw material introducing belt 6. The combustion gas generated in the fuel combustion zone 4 is supplied to the raw material introducing zone 6.
The raw material introduction belt 6 is a portion into which raw material oil is introduced. The raw material introducing belt 6 has a smaller diameter than the fuel combustion belt 4. The raw material oil introduction nozzle 5 is connected to the raw material introduction belt 6. The raw material oil is introduced into the raw material introduction belt 6 through the raw material oil introduction nozzle 5 and mixed with the combustion gas. At this time, the fine nuclei of the carbon black are formed by thermal decomposition, and collisions between the nuclei form a predetermined structure, thereby forming carbon black fine particles, which are a raw material of the carbon black. As the raw oil, aromatic hydrocarbons such as naphthalene and anthracene, coal-based hydrocarbons such as creosote oil and tar, petroleum-based heavy oils such as FCC residuum and ethylene heavy oil, acetylene-based unsaturated hydrocarbons, aliphatic hydrocarbons such as hexane, and the like are used. A mixture of combustion gas and raw oil is supplied to the reaction zone 8.
The reaction zone 8 is a portion in which the reaction is stopped after the carbon black fine particles generated in the raw material introduction zone 6 are further sufficiently vapor-grown. The diameter of the reaction zone 8 is greater than the diameter of the fuel combustion zone 4. The flow rate of the carbon black fine particles produced in the raw material introducing zone 6 decreases in the wide diameter reaction zone 8. At this time, aromatic hydrocarbons in the gas phase are carbonized and layered on the surface of the carbon black fine particles to produce a carbon black raw material. A coolant introduction nozzle 7 for stopping the reaction is provided on the downstream side of the reaction zone 8. Cooling water is sprayed from the cooling liquid introduction nozzle 7 to the reaction zone 8. Thereby, the reaction of producing the carbon black raw material is stopped.
The carbon black raw material produced in the reaction zone 8 is transferred to a collection system not shown, and collected by a collection device such as a cyclone or a bag filter.
Next, in the granulating step S2, the carbon black raw material is granulated so that the particles of the carbon black raw material reach a predetermined size. The carbon black raw material collected by the collecting device is subjected to granulation treatment. In the pelletization process, i.e., the carbon black particles are pelletized to the desired size. The specific method of the granulation treatment is not particularly limited, and a known granulation method can be applied. As a known granulation method, for example, a wet granulation method is given. An example of the wet granulation method is a method of granulating pellets of a predetermined size by continuously supplying carbon and water into a predetermined container by rotating a shaft in which a plurality of special bar pins are spirally arranged at the center of a cylinder at a high speed, and stirring and mixing the carbon and water.
Then, in the drying step S3, the granulated carbon black raw material is dried to obtain a dried carbon black raw material in order to dehydrate the granulated carbon black raw material. The specific mode of the drying treatment is not particularly limited, and a known drying method can be applied. As a known drying method, for example, an indirect heating type drying method is cited. An example of the indirect heating type drying method is a method using an indirect heating type rotary dryer. The method is a method of heating and drying a granulated carbon black raw material containing moisture disposed in an inner cylinder at a predetermined temperature by supplying hot air to a space between the outer cylinder and the inner cylinder through a rotary kiln-like double-pipe structure provided in an indirect heating type rotary dryer.
Next, in the desorption step S4, only the strongly acidic group is selectively desorbed and removed from the dry carbon black raw material to obtain carbon black. The specific mode of the release treatment is not particularly limited, and any method can be used as long as it releases and removes a strongly acidic group from carbon black. Particularly preferred method of the separation treatment is, for example, a heat treatment in an inert gas. An example of the heating treatment in the inert gas is a method in which an inert gas such as nitrogen is introduced into a fluidized bed in which a dry carbon black raw material is disposed, and the dry carbon black raw material is heated at a temperature of 300 to 400 ℃ for 5 to 30 minutes.
In the carbon black obtained by the above-described production method, the value of the DBP absorption is reduced by increasing the amount of the alkali metal salt/aqueous solution introduced in the reaction step S1. When the amount of oxygen-containing gas introduced is increased or the amount of raw oil introduced is decreased, the values of IA and N 2 SA are increased. Further, if the reaction time from introduction of the raw oil to stopping of the reaction by quenching is further shortened, the value of N 2 SA/IA becomes large.
In the desorption step S4, the degree of desorption of the concentration of the strongly acidic group can be adjusted by adjusting the temperature in the fluidized layer and the holding time in the fluidized layer.
Examples
Hereinafter, examples will be described in order to explain the present invention in more detail. However, the present invention should not be construed as being limited to the following examples.
Examples 1 to 9
The carbon black according to one embodiment of the present invention was produced in the sequence of the treatment steps shown in fig. 1. First, in the reaction step S1, a reaction furnace having the structure shown in fig. 1 was used, and the amount of fuel to be supplied, the amount of raw oil to be introduced, and the amount of air to be supplied were changed, respectively, so that 8 kinds of carbon black raw materials having different properties were produced from the time of introducing raw oil until the reaction was stopped by quenching, and the amount of alkali metal salt/aqueous solution to be introduced.
Next, in the granulation step S2, wet granulation is performed under a predetermined condition on each carbon black raw material obtained in the reaction step S1. Next, in the separation step S4, the pelletized carbon black raw material is dried under a predetermined condition using an indirect heating rotary dryer.
Next, in the separation step S4, the dry carbon black raw material was placed in the fluidized bed heated to 350 ℃, and nitrogen was introduced into the fluidized bed, and the dry carbon black raw material was allowed to remain for 10 minutes. Thus, carbon blacks of examples 1 to 9 were obtained.
Comparative examples 1 to 9
Similarly to examples 1 to 9, in the reaction step S1, a reaction furnace having the structure shown in fig. 2 was used, and the amount of fuel to be supplied, the amount of raw oil to be introduced, and the amount of air to be supplied were changed, respectively, and the reaction time from introduction of the raw oil to termination of the reaction by quenching, and the amount of alkali metal salt/aqueous solution to be introduced were changed, to produce carbon black raw materials of 9 different properties. Thereafter, the granulation step S2 and the drying step S3 were performed under the same conditions as in examples 1 to 9.
Here, unlike the cases of examples 1 to 9, the 7 carbon black raw materials were not subjected to the separation step S4. That is, the dry carbon black raw materials obtained after the drying step S3 are carbon blacks of comparative examples 1 to 5, comparative example 8 and comparative example 9.
The carbon blacks of comparative examples 1 and 2 were subjected to the separation step S4 after the drying step S3, and the carbon blacks of comparative examples 6 and 7 were obtained.
The obtained examples 1 to 9 and comparative examples 1 to 9 were measured for the amount of IA and N 2 SA, tint, DBP absorbed, the amount of 24M4DBP absorbed, and the concentration of the strongly acidic group, respectively. The measurement results are shown in tables 1 and 2, respectively.
Further, 60 parts by mass of carbon black of each of the examples and comparative examples was added to 100 parts by mass of the acrylic rubber, and the rubber compositions were adjusted.
The volume resistivity and the tensile strength of the rubber compositions with carbon black obtained in each of the examples and comparative examples were measured. Here, the volume resistivity and the tensile strength were measured by the following methods.
(Volume resistivity)
According to JIS K6271-1:2015 (calculation methods of vulcanized rubber and thermoplastic rubber-resistivity), volume resistivity VR (Ω·cm) was measured. The logarithm (LogVR) of the measured VR is shown in tables 1 and 2, respectively.
Specifically, VR was determined under the following conditions.
The measuring method comprises the following steps: double ring electrode method
Protective electrode: an outer diameter of 80mm and an inner diameter of 70mm
A main electrode: 50mm
Sample outer dimensions: 100mm by 100mm
Sampling thickness: 2mm of
Applying a voltage: 1V
Detecting the current range: 200 pA-20 mA
(Tensile Strength)
Tensile strength TB (MPa) was measured in accordance with JIS K6251-2017 (calculation method of vulcanized rubber and thermoplastic rubber-stretching characteristics). The measured TBs are shown in tables 1 and 2.
(Discussion)
The concentration of the strongly acidic groups in all the carbon blacks of examples 1to 9 was 0.50X10 -5 mol/g or less, IA was 50 to 70mg/g, N 2 SA/IA was 1.20X10 3～1.50×103m2/g, and the DBP absorption was 130 to 150cm 3/100 g.
On the other hand, the carbon blacks of comparative examples 1 to 5, comparative example 8 and comparative example 9, in which the separation step S4 was not performed, had the values of the strong acid group concentrations exceeding 0.50X10- -5 mol/g. As a result, the rubber compositions to which the carbon blacks of these comparative examples were added had inferior properties to those of the rubber compositions to which the carbon blacks of examples 1 to 9 were added.
In addition, the value of the strong acid group concentration of the carbon black of comparative example 6 obtained by further subjecting the carbon black of comparative example 1 to the separation step S4 was reduced to 0.50X10- -5 mol/g or less as compared with the carbon black of comparative example 1. In this case, when the properties of the rubber compositions to which the carbon blacks of comparative examples 1 and 6 are added are compared, the tensile strength is slightly increased when the carbon black of comparative example 6 is added, but lower than when the carbon blacks of examples 1 to 9 are added.
This is considered to be because the values of IA and N 2 SA of the carbon black of comparative example 1 are small, and the size of the carbon black particles is large, so that the adsorption of rubber molecules is insufficient.
Similarly, the value of the strong acid group concentration of the carbon black of comparative example 7 obtained by further subjecting the carbon black of comparative example 2 to the separation step S4 was reduced to 0.50×10 -5 mol/g or less as compared with the carbon black of comparative example 2. At this time, when the properties of the rubber compositions to which the carbon blacks of comparative example 2 and comparative example 7 are added are compared, the volume resistivity decreases when the carbon black of comparative example 7 is added. This value is lower than that when the carbon blacks of examples 1 to 9 are added.
This is considered to be because the carbon black of comparative example 2 has a smaller value of N 2 SA/IA, that is, a smaller amount of carbon black surface functional groups, and thus the carbon black particles easily come into close contact with each other, and the separation step S4 is performed to further promote the close contact between the carbon black particles.
Fig. 3 is a graph showing a relationship between tensile strength TB and logarithm LogVR of volume resistivity. As shown in fig. 3, the tensile strength TB and the volume resistivity of examples 1 to 9 each have a tendency to take on larger values than those of comparative examples 1 to 9.
That is, it was found that the electrical insulation and mechanical strength can be improved when the carbon black is added to rubber by limiting the concentration of the strongly acidic groups, the absorption amounts of IA, N 2 SA/IA and DBP, to the predetermined ranges.
TABLE 1
TABLE 2
Symbol description
1 … Oxygen-containing gas inlet
2 … Burner
3 … Alkali metal salt/aqueous solution supply nozzle
4 … Fuel Combustion zone
5 … Raw oil introducing nozzle
6 … Raw material introducing tape
7 … Cooling liquid introducing nozzle
8 … Reaction zone
10 … Reactor
11 … Reaction procedure
12 … Granulation Process
13 … Drying procedure
14 … Out of the process.
Claims (7)
1. A carbon black, wherein,
The concentration of the strongly acidic group is 0.50X10 -5 mol/g or less,
The iodine adsorption amount (IA) is 50-70 mg/g,
The ratio of nitrogen adsorption specific surface area (N 2 SA) to IA (N 2 SA/IA) was 1.20X10- 3～1.50×103m2/g,
The DBP absorption is 130-150 cm 3/100 g.
2. The carbon black of claim 1, wherein,
The carbon black is added as a filler to a polar rubber component.
3. The carbon black according to claim 2, wherein,
The polar rubber member is a material configured to be in contact with a metal.
4. A carbon black as claimed in claim 2 or 3, wherein,
The polar rubber component includes an acrylic rubber.
5. The carbon black according to any one of claims 2 to 4, wherein,
The carbon black is added in an amount of 30 to 90 parts by mass to 100 parts by mass of the rubber component in the polar rubber member.
6. The carbon black according to any one of claims 2 to 5, wherein,
The polar rubber member is an automotive member.
7. A method of making carbon black comprising:
A step of incompletely combusting the hydrocarbon raw material to produce a carbon black raw material; and
And heating the carbon black raw material at 300 to 400 ℃ in an inert gas atmosphere.
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| JP3456759B2 (en) * | 1994-06-09 | 2003-10-14 | 東海カーボン株式会社 | Furnace carbon black |
| JP3922962B2 (en) * | 2002-04-18 | 2007-05-30 | 東海カーボン株式会社 | Carbon black for compounding functional rubber parts |
| JP2004323551A (en) * | 2003-04-21 | 2004-11-18 | Sumitomo Dow Ltd | Electroconductive polycarbonate resin composition and molded article composed thereof |
| DE102009045060A1 (en) * | 2009-09-28 | 2011-03-31 | Evonik Degussa Gmbh | Carbon black, a process for its preparation and its use |
| JP6684607B2 (en) * | 2016-02-19 | 2020-04-22 | 東海カーボン株式会社 | Carbon black, method for producing carbon black, and rubber composition |
| CN115443315A (en) * | 2021-04-02 | 2022-12-06 | 东海炭素株式会社 | Carbon black and process for producing carbon black |
| JP7364615B2 (en) * | 2021-04-02 | 2023-10-18 | 住友理工株式会社 | Rubber compositions, rubber products using the same, and hoses |
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