CN116396626B - Modified white carbon black and preparation method thereof - Google Patents
Modified white carbon black and preparation method thereof Download PDFInfo
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- CN116396626B CN116396626B CN202310306340.6A CN202310306340A CN116396626B CN 116396626 B CN116396626 B CN 116396626B CN 202310306340 A CN202310306340 A CN 202310306340A CN 116396626 B CN116396626 B CN 116396626B
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- 239000006229 carbon black Substances 0.000 title claims abstract description 76
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims abstract description 32
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims abstract description 21
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 20
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 15
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 15
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 15
- PBIDWHVVZCGMAR-UHFFFAOYSA-N 1-methyl-3-prop-2-enyl-2h-imidazole Chemical compound CN1CN(CC=C)C=C1 PBIDWHVVZCGMAR-UHFFFAOYSA-N 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 55
- 239000000203 mixture Substances 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 37
- 239000005060 rubber Substances 0.000 abstract description 37
- 238000004132 cross linking Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 235000019241 carbon black Nutrition 0.000 description 61
- 230000000052 comparative effect Effects 0.000 description 18
- 238000005299 abrasion Methods 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- -1 papermaking Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical group CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- 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
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- 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
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3063—Treatment with low-molecular organic compounds
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- 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
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3072—Treatment with macro-molecular organic compounds
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- 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
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3081—Treatment with organo-silicon compounds
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- 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
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
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- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention relates to modified white carbon black and a preparation method thereof, and belongs to the technical field of white carbon black preparation. In the preparation process of the modified white carbon black, cetyl trimethyl ammonium bromide and n-octyl triethoxysilane are added to perform a synergistic effect, so that the surface energy of the white carbon black is reduced, the compatibility with a polymer is improved, and the dispersibility of the modified white carbon black in rubber is more effectively improved; the invention also adds 1-allyl-3-methylimidazole chloride, which increases the physical crosslinking points between the effectively dispersed modified white carbon black and the rubber molecular chain based on the effects of hexadecyl trimethyl ammonium bromide and n-octyl triethoxysilane, and improves the crosslinking network structure, thereby improving the wear resistance; the added aliphatic polyoxyethylene ether helps to maintain the stability of the 2-mercaptobenzothiazole in the modified white carbon black, so that the molecular chain of the rubber is restricted when being stressed, and the tensile strength is increased.
Description
Technical Field
The invention belongs to the technical field of white carbon black preparation, and particularly relates to modified white carbon black and a preparation method thereof.
Background
White carbon black is a white, nontoxic and amorphous fine powder, has super-strong adhesive force and tear resistance, heat resistance and ageing resistance, is mainly used as a filler of products such as rubber, plastics, papermaking, paint coating and the like, and is an important fine inorganic chemical product. The second largest rubber reinforcing agent is inferior to carbon black because of the characteristics of low price, good reinforcing performance, large filling amount and the like, and the reinforcing effect is far superior to other white fillers. Currently, about 70% of white carbon black is used in the rubber industry to obtain high quality rubber products such as off-road tires, engineering tires, radial tires, and the like. White carbon black has many excellent properties including porosity, good dispersibility, non-combustion, good chemical stability, etc. as an inorganic filler, and is thus widely used as a filler for toothpastes, paints, plastics, rubber, etc.; and as a reinforcing agent, the white carbon black can improve the mechanical property of the tire rubber and reduce the rolling resistance of the tire rubber. Nowadays, more and more manufacturers gradually apply white carbon black instead of carbon black.
However, the traditional white carbon black is easy to agglomerate, and also causes the problems of hydrophilicity, easy adsorption of a compounding agent in rubber, weak wear resistance and tensile strength reinforcement of rubber and the like, so that the reinforcement performance in rubber is seriously influenced, and the increasingly-growing quality requirements of masses on rubber can not be met. Therefore, the surface of the white carbon black is modified to improve the application effect and the added value of the white carbon black, so that the application field of the product is expanded, and the white carbon black has become a research hot spot in recent years.
Disclosure of Invention
The invention aims to provide modified white carbon black and a preparation method thereof, wherein cetyl trimethyl ammonium bromide and n-octyl triethoxysilane are added in the preparation process of the modified white carbon black to act synergistically, so that the surface energy of the white carbon black is reduced, the compatibility with polymers is improved, and the dispersibility of the modified white carbon black in rubber is more effectively improved; the invention also adds 1-allyl-3-methylimidazole chloride, which increases the physical crosslinking points between the effectively dispersed white carbon black and the rubber molecular chain based on the effects of hexadecyl trimethyl ammonium bromide and n-octyl triethoxysilane, and improves the crosslinking network structure, thereby improving the wear resistance; the added aliphatic polyoxyethylene ether helps to maintain the stability of the 2-mercaptobenzothiazole in the white carbon black, so that the molecular chain of the rubber is restricted when being stressed so as to increase the tensile strength, and the problem that the white carbon black in the prior art is poor in wear resistance and tensile strength reinforcing effect when applied to the rubber is solved.
The aim of the invention can be achieved by the following technical scheme:
the modified white carbon black comprises the following raw materials in parts by weight:
according to the invention, the cetyl trimethyl ammonium bromide and the n-octyl triethoxysilane are added, and after being added into a reaction system, the cetyl trimethyl ammonium bromide interacts with the white carbon black and adheres to the surface of the white carbon black, so that a large amount of active hydroxyl on the surface of the white carbon black is consumed, and at the same time, the n-octyl triethoxysilane acts synergistically, and an organic group with low surface energy at one end of the n-octyl triethoxysilane further modifies the white carbon black, so that the surface energy of the white carbon black is reduced, the compatibility with a polymer is improved, the dispersibility of the white carbon black in rubber is more effectively improved, and the durability of a product is enhanced. On the basis of the effects of cetyl trimethyl ammonium bromide and n-octyl triethoxysilane, the 1-allyl-3-methylimidazole chloride increases physical crosslinking points between effectively dispersed white carbon black and rubber molecular chains, and the crosslinked network structure is more perfect, so that the external force can be effectively transmitted and dispersed when the external force acts, the breakage of the rubber molecular chains is reduced, and the wear resistance is improved.
Further, the preparation method of the modified white carbon black comprises the following steps:
s1, mixing white carbon black, deionized water and cetyltrimethylammonium bromide, and uniformly stirring at a controlled temperature to obtain a mixture A for later use; mixing and stirring n-octyl triethoxysilane and ethanol to obtain a mixture B for later use;
s2, mixing the mixture A and the mixture B prepared in the step S1, controlling the temperature, mechanically stirring, maintaining the temperature after stirring, sequentially adding sodium hydroxide and 1-allyl-3-methylimidazole chloride, and mechanically stirring to obtain a mixture C;
and S3, adding the aliphatic polyoxyethylene ether into the mixture C obtained in the step S2, stirring at a controlled temperature, adding the 2-mercaptobenzothiazole after stirring, stirring at a controlled temperature, filtering, washing and drying the product after stirring, and obtaining the modified white carbon black.
According to the invention, 2-mercaptobenzothiazole and aliphatic polyoxyethylene ether are added, and the aliphatic polyoxyethylene ether is assisted to maintain the stability of the 2-mercaptobenzothiazole in the white carbon black, so that the white carbon black and a rubber molecular chain are chemically combined, a cross-linked network is enhanced and formed, and the rubber molecular chain is restricted when being stressed so as to increase the tensile strength.
Further, the temperature of the temperature-controlled stirring uniform in the step S1 is 65-70 ℃; the mixing and stirring time is 60-70min.
Further, the temperature of the temperature control in the step S2 is 70-75 ℃; the mechanical stirring speed of the two times is 280-300r/min, and the stirring time is 1-1.5h and 20-30min respectively.
Further, the temperature of the two-time temperature-controlled stirring in the step S3 is 40-45 ℃ and 100-110 ℃ respectively, and the stirring time is 10-15min and 60-80min respectively; the temperature of the temperature-controlled drying is 105-110 ℃.
The invention has the beneficial effects that:
(1) According to the invention, the cetyl trimethyl ammonium bromide and the n-octyl triethoxysilane are added, and after being added into a reaction system, the cetyl trimethyl ammonium bromide interacts with the white carbon black and adheres to the surface of the white carbon black, so that a large amount of active hydroxyl on the surface of the white carbon black is consumed, and at the same time, the n-octyl triethoxysilane synergistically acts, and an organic group with low surface energy at one end of the n-octyl triethoxysilane further modifies the white carbon black, so that the surface energy of the white carbon black is reduced, the compatibility with a polymer is improved, the dispersibility of the modified white carbon black in rubber is more effectively improved, and the durability of a product is enhanced.
(2) The addition of the 1-allyl-3-methylimidazole chloride increases the physical crosslinking points between the effectively dispersed modified white carbon black and the rubber molecular chain on the basis of the effects of cetyl trimethyl ammonium bromide and n-octyl triethoxysilane, so that the crosslinked network structure is more perfect, and the external force can be effectively transmitted and dispersed when the external force acts, and the breakage of the rubber molecular chain is reduced, thereby improving the wear resistance.
(3) According to the invention, the 2-mercaptobenzothiazole and the aliphatic polyoxyethylene ether are added, and the aliphatic polyoxyethylene ether is assisted to maintain the stability of the 2-mercaptobenzothiazole in the white carbon black, so that the 2-mercaptobenzothiazole is chemically combined between the modified white carbon black and a rubber molecular chain, and a cross-linked network is formed by enhancement, and the rubber molecular chain is restricted when being stressed so as to increase the tensile strength.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The 1-allyl-3-methylimidazole chloride salt used in the invention has the product number of A74920-25g and is purchased from Shanghai Jizhui Biochemical technology Co., ltd; 2-mercaptobenzothiazole, cat# 2054213, purchased from Shandong Living Biotechnology Co., ltd; the aliphatic polyoxyethylene ether is AEO-9, and is purchased from Guangzhou Honghai chemical industry Co., ltd; the details are not described in detail later.
Example 1
Weighing the following raw materials in parts by weight:
the preparation method of the modified white carbon black comprises the following steps:
s1, mixing white carbon black, deionized water and cetyltrimethylammonium bromide, and uniformly stirring at a temperature of 68 ℃ to obtain a mixture A for later use; mixing and stirring n-octyl triethoxysilane and ethanol for 60min to obtain a mixture B for later use;
s2, mixing the mixture A and the mixture B prepared in the step S1, controlling the temperature to be 75 ℃, controlling the speed to be 280r/min, mechanically stirring for 1.5 hours, maintaining the temperature after stirring, sequentially adding sodium hydroxide and 1-allyl-3-methylimidazole chloride, and controlling the speed to be 290r/min, and mechanically stirring for 20 minutes to obtain a mixture C;
and S3, adding aliphatic polyoxyethylene ether into the mixture C obtained in the step S2, stirring for 15min at the temperature of 43 ℃, adding 2-mercaptobenzothiazole after stirring, stirring for 60min at the temperature of 105 ℃, filtering and washing the product after stirring, and drying at the temperature of 110 ℃ to obtain the modified white carbon black.
Example 2
Weighing the following raw materials in parts by weight:
the preparation method of the modified white carbon black comprises the following steps:
s1, mixing white carbon black, deionized water and cetyltrimethylammonium bromide, and uniformly stirring at a temperature of 65 ℃ to obtain a mixture A for later use; mixing and stirring n-octyl triethoxysilane and ethanol for 70min to obtain a mixture B for later use;
s2, mixing the mixture A and the mixture B prepared in the step S1, controlling the temperature to be 73 ℃, controlling the speed to be 300r/min, mechanically stirring for 1h, maintaining the temperature after stirring, sequentially adding sodium hydroxide and 1-allyl-3-methylimidazole chloride, and controlling the speed to be 280r/min, and mechanically stirring for 30min to obtain a mixture C;
and S3, adding aliphatic polyoxyethylene ether into the mixture C obtained in the step S2, stirring for 13min at the temperature of 45 ℃, adding 2-mercaptobenzothiazole after stirring, stirring for 80min at the temperature of 100 ℃, filtering and washing the product after stirring, and drying at the temperature of 105 ℃ to obtain the modified white carbon black.
Example 3
Weighing the following raw materials in parts by weight:
the preparation method of the modified white carbon black comprises the following steps:
s1, mixing white carbon black, deionized water and cetyltrimethylammonium bromide, and uniformly stirring at a temperature of 70 ℃ to obtain a mixture A for later use; mixing and stirring n-octyl triethoxysilane and ethanol for 65min to obtain a mixture B for later use;
s2, mixing the mixture A and the mixture B prepared in the step S1, controlling the temperature to be 70 ℃, controlling the speed to be 290r/min, mechanically stirring for 1h, maintaining the temperature after stirring, sequentially adding sodium hydroxide and 1-allyl-3-methylimidazole chloride, and controlling the speed to be 300r/min, and mechanically stirring for 25min to obtain a mixture C;
and S3, adding aliphatic polyoxyethylene ether into the mixture C obtained in the step S2, stirring for 10min at the temperature of 40 ℃, adding 2-mercaptobenzothiazole after stirring, stirring for 70min at the temperature of 110 ℃, filtering and washing the product after stirring, and drying at the temperature of 110 ℃ to obtain the modified white carbon black.
Comparative examples 1 to 3
The difference compared with example 3 is that the comparative examples 1 to 3 are shown in Table 1 in parts by weight of n-octyltriethoxysilane, cetyltrimethylammonium bromide and 1-allyl-3-methylimidazole chloride, and the amounts of the remaining raw materials, the operating procedures and the parameters are the same.
TABLE 1
Comparative example 4
The difference compared with example 3 is that the 2-mercaptobenzothiazole is 0.5 part by weight, and the amounts of the remaining raw materials, the operation steps and the parameters are the same.
Comparative example 5
The difference compared with example 3 is that the 2-mercaptobenzothiazole is 1.4 parts by weight, and the amounts of the remaining raw materials, the operating procedures and the parameters are the same.
Comparative example 6
Compared with example 3, the difference is that the aliphatic polyoxyethylene ether is 5 parts by weight, and the other raw materials are the same in dosage, operation steps and parameters.
Comparative example 7
Compared with example 3, the difference is that the aliphatic polyoxyethylene ether is 10 parts by weight, and the other raw materials are the same in dosage, operation steps and parameters.
Test case
The modified white carbon blacks obtained in examples 1 to 3 and comparative examples 1 to 7 were added to rubber, respectively, and rubber tests were conducted using styrene-butadiene rubber as the rubber, and the specific formulation and processing method were as follows: 100g of raw material styrene-butadiene rubber, 5g of zinc oxide, 1.5g of sulfur, 2g of accelerator CZ, 0.5 g of accelerator DM, 20g of modified white carbon black and 2g of stearic acid are uniformly mixed, then the mixture is injected into an internal mixer, the mixture is heated for 25min at 80 ℃ under the vacuum of-0.7 MPa, then the mixture is cooled to 50 ℃ and heated for 1.5h, then the mixture is reversely refined and heat treated for 7min on an open mill, then the mixture is placed on a flat vulcanizing machine and vulcanized for 25min at 160 ℃, the vulcanizing pressure is 10MPa, the obtained styrene-butadiene rubber is stood for 24h after die sinking, and then the obtained styrene-butadiene rubber is subjected to abrasion resistance and tensile strength test.
(1) Abrasion resistance test: the styrene-butadiene rubber prepared in examples 1-3 and comparative examples 1-3 were subjected to an acle abrasion volume test using an acle abrasion tester of Dongguan medical laboratory equipment Co., ltd. Model HB-7008 according to standard GB/T1689-1998, and the results are shown in Table 2.
(2) Tensile strength test: the tensile strength of the styrene-butadiene rubber prepared in examples 1 to 3 and comparative examples 4 to 7 was measured by a tensile tester of the Dongguan power display instrument technology Co.Ltd.model HZ-1003B according to the standard GB/T528-2009, and the results are shown in Table 2.
TABLE 2
| Acle abrasion volume (Cm) 3 ·1.61km -1 ) | Tensile Strength (MPa) | |
| Example 1 | 0.841 | 16.6 |
| Example 2 | 0.848 | 16.7 |
| Example 3 | 0.837 | 16.9 |
| Comparative example 1 | 0.913 | —— |
| Comparative example 2 | 0.978 | —— |
| Comparative example 3 | 0.996 | —— |
| Comparative example 4 | —— | 15.5 |
| Comparative example 5 | —— | 15.6 |
| Comparative example 6 | —— | 16.1 |
| Comparative example 7 | —— | 16.0 |
As can be seen from Table 2, the modified white carbon black prepared by the invention has excellent reinforcing effect, and the abrasion resistance and tensile strength of the product can be improved effectively when the modified white carbon black is added into rubber. In detail, as shown in comparative examples 1-3, the invention adds hexadecyl trimethyl ammonium bromide and n-octyl triethoxysilane, and after the hexadecyl trimethyl ammonium bromide is added into a reaction system, the hexadecyl trimethyl ammonium bromide and the n-octyl triethoxysilane act cooperatively, so that the surface energy of the white carbon black is reduced, the compatibility with polymers is improved, and the dispersibility of the modified white carbon black in rubber is more effectively improved; the invention also adds 1-allyl-3-methylimidazole chloride, which increases the physical crosslinking point between the effectively dispersed modified white carbon black and the rubber molecular chain based on the effects of hexadecyl trimethyl ammonium bromide and n-octyl triethoxysilane, has more perfect crosslinking network structure, can effectively transfer and disperse external force when being acted by external force, reduces the breakage of the rubber molecular chain, and further improves the wear resistance.
As can be seen from comparative examples 3-7, the added aliphatic polyoxyethylene ether of the invention helps to maintain the stability of the 2-mercaptobenzothiazole in the white carbon black, so that the modified white carbon black and the rubber molecular chain are combined chemically, a crosslinked network is enhanced and formed, and the rubber molecular chain is restricted when being stressed so as to increase the tensile strength.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (4)
1. The modified white carbon black is characterized by comprising the following raw materials in parts by weight:
the preparation method of the modified white carbon black comprises the following steps:
s1, mixing white carbon black, deionized water and cetyltrimethylammonium bromide, and uniformly stirring at a controlled temperature to obtain a mixture A for later use; mixing and stirring n-octyl triethoxysilane and ethanol to obtain a mixture B for later use;
the temperature of the temperature-controlled stirring is 65-70 ℃; the mixing and stirring time is 60-70min;
s2, mixing the mixture A and the mixture B prepared in the step S1, controlling the temperature, mechanically stirring, maintaining the temperature after stirring, sequentially adding sodium hydroxide and 1-allyl-3-methylimidazole chloride, and mechanically stirring to obtain a mixture C;
the temperature of the temperature control is 70-75 ℃;
and S3, adding the aliphatic polyoxyethylene ether into the mixture C obtained in the step S2, stirring at a controlled temperature, adding the 2-mercaptobenzothiazole after stirring, stirring at a controlled temperature, filtering, washing and drying the product after stirring, and obtaining the modified white carbon black.
2. The modified white carbon black according to claim 1, wherein the mechanical stirring speed of the two times in the step S2 is 280-300r/min, and the stirring time is 1-1.5h and 20-30min respectively.
3. The modified white carbon black according to claim 1, wherein the temperature of the two temperature-controlled stirring in the step S3 is 40-45 ℃ and 100-110 ℃ respectively, and the stirring time is 10-15min and 60-80min respectively.
4. The modified white carbon black of claim 1, wherein the temperature of the temperature-controlled drying in step S3 is 105-110 ℃.
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Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19617039A1 (en) * | 1995-06-01 | 1996-12-05 | Degussa | Precipitated silicas, process for their preparation and use of vulcanizable rubber mixtures |
| CN103275365A (en) * | 2013-06-20 | 2013-09-04 | 南京理工大学 | A kind of ionic liquid modified carbon black-silica dual-phase particle filled natural rubber and preparation method thereof |
| JP2013234268A (en) * | 2012-05-09 | 2013-11-21 | Olympus Corp | Composite rubber material, molding, and method for manufacturing composite rubber material |
| JP2016074810A (en) * | 2014-10-06 | 2016-05-12 | 住友ゴム工業株式会社 | Rubber composition and pneumatic tire |
| CN106832417A (en) * | 2017-03-14 | 2017-06-13 | 北京化工大学 | Using aliphatic APEO modified white carbon black and its with rubber combined method |
| CN107686564A (en) * | 2017-10-30 | 2018-02-13 | 无锡恒诚硅业有限公司 | A kind of preparation method of hydrophabic silica |
| CN108659271A (en) * | 2018-04-19 | 2018-10-16 | 金华市博益飞科技有限公司 | Glue bottom and preparation method thereof with good wear performance |
| CN109135345A (en) * | 2018-08-01 | 2019-01-04 | 安徽锦华氧化锌有限公司 | A kind of method of the rubber product anti-old coupling agent modified Nano carbon white of ionic liquid- |
| CN109734960A (en) * | 2019-01-08 | 2019-05-10 | 华南理工大学 | Application of a Modified Silica in Combined Rubber |
| CN109942003A (en) * | 2019-04-17 | 2019-06-28 | 华东理工大学 | A kind of method of dry grinding modified precipitated silica |
| CN110054914A (en) * | 2019-04-18 | 2019-07-26 | 常州大学 | A kind of preparation method of hydrophobicity high abrasion white carbon black |
| CN110092801A (en) * | 2019-01-07 | 2019-08-06 | 青岛科技大学 | A kind of novel promotion silane coupling agent and preparation method thereof |
| CN110734594A (en) * | 2018-07-19 | 2020-01-31 | 中国石油天然气股份有限公司 | Method for preparing emulsion polymerized styrene butadiene rubber from modified carbon blacks |
| CN111073062A (en) * | 2019-12-16 | 2020-04-28 | 宿迁德特材料科技有限公司 | Preparation method of high-strength wet-skid-resistant tread rubber material |
| CN111218045A (en) * | 2020-03-24 | 2020-06-02 | 青岛科技大学 | A kind of room temperature modified silica reinforced styrene-butadiene rubber and preparation method of compound rubber |
| CN112175418A (en) * | 2019-07-05 | 2021-01-05 | 北京化工大学 | A kind of modified white carbon black and its preparation method and masterbatch |
| CN113150389A (en) * | 2021-04-27 | 2021-07-23 | 三明学院 | Preparation method of hydrophobic white carbon black |
| CN113501979A (en) * | 2021-07-15 | 2021-10-15 | 江南大学 | High-temperature water-soluble fiber-opening sea-island fiber fabric and preparation method thereof |
| CN114286801A (en) * | 2021-12-01 | 2022-04-05 | 无锡恒诚硅业有限公司 | Hydrophobic high-dispersion white carbon black and preparation method and application thereof |
| CN114286800A (en) * | 2021-12-01 | 2022-04-05 | 无锡恒诚硅业有限公司 | Hydrophobic white carbon black rubber reinforcing agent and preparation method and application thereof |
| CN114316369A (en) * | 2022-01-05 | 2022-04-12 | 湖北江瀚新材料股份有限公司 | Modified white carbon black and preparation method thereof |
| CN115197471A (en) * | 2021-04-12 | 2022-10-18 | 北京化工大学 | A kind of preparation method of modified graphene/silica composite filler, composite filler and rubber composite material, and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8003724B2 (en) * | 2009-07-07 | 2011-08-23 | The Goodyear Tire & Rubber Company | Specialized silica, rubber composition containing specialized silica and products with component thereof |
-
2023
- 2023-03-27 CN CN202310306340.6A patent/CN116396626B/en active Active
Patent Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19617039A1 (en) * | 1995-06-01 | 1996-12-05 | Degussa | Precipitated silicas, process for their preparation and use of vulcanizable rubber mixtures |
| JP2013234268A (en) * | 2012-05-09 | 2013-11-21 | Olympus Corp | Composite rubber material, molding, and method for manufacturing composite rubber material |
| CN103275365A (en) * | 2013-06-20 | 2013-09-04 | 南京理工大学 | A kind of ionic liquid modified carbon black-silica dual-phase particle filled natural rubber and preparation method thereof |
| JP2016074810A (en) * | 2014-10-06 | 2016-05-12 | 住友ゴム工業株式会社 | Rubber composition and pneumatic tire |
| CN106832417A (en) * | 2017-03-14 | 2017-06-13 | 北京化工大学 | Using aliphatic APEO modified white carbon black and its with rubber combined method |
| CN107686564A (en) * | 2017-10-30 | 2018-02-13 | 无锡恒诚硅业有限公司 | A kind of preparation method of hydrophabic silica |
| CN108659271A (en) * | 2018-04-19 | 2018-10-16 | 金华市博益飞科技有限公司 | Glue bottom and preparation method thereof with good wear performance |
| CN110734594A (en) * | 2018-07-19 | 2020-01-31 | 中国石油天然气股份有限公司 | Method for preparing emulsion polymerized styrene butadiene rubber from modified carbon blacks |
| CN109135345A (en) * | 2018-08-01 | 2019-01-04 | 安徽锦华氧化锌有限公司 | A kind of method of the rubber product anti-old coupling agent modified Nano carbon white of ionic liquid- |
| CN110092801A (en) * | 2019-01-07 | 2019-08-06 | 青岛科技大学 | A kind of novel promotion silane coupling agent and preparation method thereof |
| CN109734960A (en) * | 2019-01-08 | 2019-05-10 | 华南理工大学 | Application of a Modified Silica in Combined Rubber |
| CN109942003A (en) * | 2019-04-17 | 2019-06-28 | 华东理工大学 | A kind of method of dry grinding modified precipitated silica |
| CN110054914A (en) * | 2019-04-18 | 2019-07-26 | 常州大学 | A kind of preparation method of hydrophobicity high abrasion white carbon black |
| CN112175418A (en) * | 2019-07-05 | 2021-01-05 | 北京化工大学 | A kind of modified white carbon black and its preparation method and masterbatch |
| CN111073062A (en) * | 2019-12-16 | 2020-04-28 | 宿迁德特材料科技有限公司 | Preparation method of high-strength wet-skid-resistant tread rubber material |
| CN111218045A (en) * | 2020-03-24 | 2020-06-02 | 青岛科技大学 | A kind of room temperature modified silica reinforced styrene-butadiene rubber and preparation method of compound rubber |
| CN115197471A (en) * | 2021-04-12 | 2022-10-18 | 北京化工大学 | A kind of preparation method of modified graphene/silica composite filler, composite filler and rubber composite material, and preparation method thereof |
| CN113150389A (en) * | 2021-04-27 | 2021-07-23 | 三明学院 | Preparation method of hydrophobic white carbon black |
| CN113501979A (en) * | 2021-07-15 | 2021-10-15 | 江南大学 | High-temperature water-soluble fiber-opening sea-island fiber fabric and preparation method thereof |
| CN114286801A (en) * | 2021-12-01 | 2022-04-05 | 无锡恒诚硅业有限公司 | Hydrophobic high-dispersion white carbon black and preparation method and application thereof |
| CN114286800A (en) * | 2021-12-01 | 2022-04-05 | 无锡恒诚硅业有限公司 | Hydrophobic white carbon black rubber reinforcing agent and preparation method and application thereof |
| CN114316369A (en) * | 2022-01-05 | 2022-04-12 | 湖北江瀚新材料股份有限公司 | Modified white carbon black and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张旭敏.离子液体与白炭黑的相互作用及其对天然橡胶性能的影响.《合成橡胶工业》.2016,第39卷(第5期),404-408. * |
| 张皓文.硅烷偶联剂KH570和CTAB协同改性白炭黑及其应用.《现代化工》.2020,第40卷(第3期),88-91. * |
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