CN116987322A - Preparation method of anti-precipitation anti-aging agent - Google Patents
Preparation method of anti-precipitation anti-aging agent Download PDFInfo
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- CN116987322A CN116987322A CN202310808521.9A CN202310808521A CN116987322A CN 116987322 A CN116987322 A CN 116987322A CN 202310808521 A CN202310808521 A CN 202310808521A CN 116987322 A CN116987322 A CN 116987322A
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- aging agent
- precipitation
- cardanol
- rubber
- modified cardanol
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- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 96
- 238000001556 precipitation Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 95
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims abstract description 54
- 229920001971 elastomer Polymers 0.000 claims abstract description 48
- 239000002904 solvent Substances 0.000 claims abstract description 46
- 239000007787 solid Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims abstract description 17
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims abstract description 17
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 13
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000013329 compounding Methods 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000006229 carbon black Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 18
- 239000012295 chemical reaction liquid Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000012744 reinforcing agent Substances 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 239000002994 raw material Substances 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 239000004636 vulcanized rubber Substances 0.000 description 7
- 244000043261 Hevea brasiliensis Species 0.000 description 6
- 235000021355 Stearic acid Nutrition 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 6
- 229920003052 natural elastomer Polymers 0.000 description 6
- 229920001194 natural rubber Polymers 0.000 description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 6
- 238000010057 rubber processing Methods 0.000 description 6
- 239000008117 stearic acid Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 cardanol aromatic amine Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- 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
- C08K5/16—Nitrogen-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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of an anti-precipitation anti-aging agent, which comprises the steps of dissolving cardanol, paraformaldehyde and para-aminodiphenylamine in a solvent according to a certain proportion, heating and reacting to obtain a reaction solution containing modified cardanol, and uniformly mixing and compounding the modified cardanol and a solid load to obtain the anti-precipitation anti-aging agent. According to the invention, modified cardanol is used as an anti-aging agent, and on one hand, double bonds on side groups of cardanol can participate in rubber crosslinking to inhibit precipitation of the modified cardanol anti-aging agent; on the other hand, by compounding the modified cardanol with a conventional reinforcing agent for rubber, the reinforcing agent enhances the rubber performance, and simultaneously, the precipitation of the bio-based modified cardanol loaded on the surface of the reinforcing agent is further slowed down through space resistance, so that the existing anti-aging agent is easy to precipitate, and the anti-aging agent with a single large space structure is easy to influence the rubber performance.
Description
Technical Field
The invention belongs to the technical field of modification of rubber additives, and particularly relates to a preparation method of an anti-precipitation anti-aging agent.
Background
In the prior art, the antioxidant is an indispensable additive in rubber products, and can endow the rubber with excellent weather resistance, longer service life and higher use value. In recent years, in order to develop environment-friendly rubber antioxidants, many natural antioxidants are further improved and applied to rubber products, and become an important development trend of rubber antioxidants.
However, the existing anti-aging agent has an migration phenomenon, which can cause physical loss of the anti-aging agent, so that the protection effect of the anti-aging agent is greatly weakened, and in order to solve the problem, the solutions reported in the prior literature comprise loading the anti-aging agent on nano-fillers, synthesizing the macromolecular anti-aging agent and preparing the anti-aging agent with a large space structure. For example, CN202211237604.9 is a macromolecular anti-precipitation heat-resistant anti-aging agent which is prepared by carrying out modification treatment after loading the anti-aging agent on a porous medium and bonding with a synthetic product of ethylenediamine and methyl acrylate. According to the preparation method, the porous medium is used for carrying the anti-aging agent and then is modified, the porous medium is bonded with a synthesized product of ethylenediamine and methyl acrylate, the interface contact area of the anti-aging agent and each component in the matrix material is greatly increased, the bonding strength is enhanced, the movement of the anti-aging agent in the matrix material is limited, the precipitation of the anti-aging agent is restrained, and the macromolecular anti-precipitation heat-resistant anti-aging agent is connected with each other, so that a multi-layer anti-aging agent layer formed by a framework in the matrix material can resist the corrosion of various external factors in a layered manner, the aging process of the matrix material can be effectively delayed, and the storage period and the service life of the matrix material are prolonged. Although these methods slow down the migration of the anti-aging agents to some extent, their preparation process is complicated and the synthesis conditions are high. And the anti-aging agent is not cooperated with the raw material of the original rubber, and the addition of the anti-aging agent with extra large particles can influence the performance of the rubber.
Disclosure of Invention
The invention provides reinforced modified rubber and a preparation method thereof, which aim to solve the problems that the existing anti-aging agent is easy to separate out, and the single anti-aging agent with a large space structure can delay the separation of the anti-aging agent, but the large particles of the anti-aging agent can influence the rubber performance.
The invention is realized by the following technical scheme:
the preparation method of the anti-precipitation anti-aging agent comprises the following preparation steps: and (3) dissolving cardanol, paraformaldehyde and para-aminodiphenylamine in a solvent according to a certain proportion, heating and reacting to obtain a black reaction solution containing modified cardanol, uniformly mixing the modified cardanol with a solid carrier, and compounding to obtain the anti-precipitation anti-aging agent.
Further, the solid carrier is white carbon black, and the white carbon black is inorganic micro/nano particles, and is used as a conventional reinforcing agent for rubber, and contains a large number of acidic Si-OH bonds, so that the surface of the solid carrier is required to be modified to improve the compatibility with the rubber, and the process is increased. According to the invention, the white carbon black and the cardanol aromatic amine anti-aging agent are compounded by utilizing the interaction of the alkaline NH bond of the aromatic amine and Si-OH, so that on one hand, the acidity of the white carbon black is eliminated, and the process for modifying the white carbon black is reduced; on the other hand, the white carbon black has larger particles, can further increase the precipitation resistance of the modified cardanol anti-aging agent, and does not influence the performance of the rubber by adding large particles.
Further, the mass ratio of the cardanol to the paraformaldehyde to the para-aminodiphenylamine is 1-2:1:0.9-1.05.
Further, the temperature of the heating reaction is 30-140 ℃, and the reaction time is 1-24h.
Further, the specific steps of compounding the modified cardanol with the solid carrier include: adding a solid load into the black reaction liquid containing the modified cardanol, stirring and mixing uniformly, and removing the solvent to obtain the solid anti-precipitation anti-aging agent.
Further, the specific steps of compounding the modified cardanol with the solid carrier include: removing the solvent from the black reaction solution containing the modified cardanol to obtain the modified cardanol, dissolving the modified cardanol in a volatile solvent, adding a solid load, stirring and mixing uniformly, and removing the volatile solvent to obtain the solid anti-precipitation anti-aging agent.
Further, the specific steps of compounding the modified cardanol with the solid carrier include: removing the solvent from the black reaction solution containing the modified cardanol to obtain the modified cardanol, mixing the modified cardanol with a solid carrier, and sufficiently grinding to obtain the solid anti-precipitation anti-aging agent.
Further, the mass ratio of the modified cardanol to the solid load is 0.1-10:1.
Further, the anti-precipitation anti-aging agent is applied to rubber.
Compared with the prior art, the beneficial effects are that:
according to the invention, modified cardanol is used as an anti-aging agent, and unsaturated double bonds of side chains of cardanol can participate in rubber vulcanization crosslinking reaction, so that the modified cardanol has certain anti-precipitation performance. Meanwhile, the modified cardanol and the conventional reinforcing agent of the rubber are compounded to obtain the composite anti-aging agent, so that the precipitation of the bio-based modified cardanol loaded on the surface of the rubber is further slowed down through space resistance while the reinforcing agent enhances the rubber performance, and the aging resistance and the service life of a rubber product are improved.
Drawings
FIG. 1 is a graph showing the change in tensile strength of a rubber sheet at various times of thermal oxidative aging.
Detailed Description
The present invention is further illustrated and described below with reference to examples, which are not intended to be limiting in any way. Unless otherwise indicated, the methods and apparatus used in the examples were conventional in the art and the starting materials used were all conventional commercially available.
Example 1
The embodiment provides a preparation method of an anti-precipitation anti-aging agent, which comprises the following preparation steps:
the cardanol, the paraformaldehyde and the para-aminodiphenylamine are weighed according to the proportion of 1.25:1:0.95, then are added into a three-neck flask, and a proper amount of alcohol solution and petroleum ether solvent are measured by a measuring cylinder and added into the three-neck flask, so that raw materials are dissolved. Then the three-neck flask is placed in an oil bath pot, the temperature is set to be 30-140 ℃, the reaction is carried out for 1-24 hours, and the finished reaction liquid is black liquid.
Removing the solvent of the black reaction liquid to obtain a bio-based anti-aging agent, adding an ethyl acetate volatile solvent to dissolve a bio-based anti-aging agent product, adding white carbon black while stirring successively, wherein the ratio of the bio-based anti-aging agent to the white carbon black is 5:1, and removing the solvent after stirring uniformly to obtain the solid anti-precipitation anti-aging agent A.
Example 2
The embodiment provides a preparation method of an anti-precipitation anti-aging agent, which comprises the following preparation steps:
the cardanol, the paraformaldehyde and the para-aminodiphenylamine are weighed according to the proportion of 1.25:1:0.95, then are added into a three-neck flask, and a proper amount of alcohol solution and petroleum ether solvent are measured by a measuring cylinder and added into the three-neck flask, so that raw materials are dissolved. Then the three-neck flask is placed in an oil bath pot, the temperature is set to be 30-140 ℃, the reaction is carried out for 1-24 hours, and the finished reaction liquid is black liquid.
Adding ethyl acetate volatile solvent into the black reaction solution, adding white carbon black successively while stirring, wherein the ratio of the bio-based anti-aging agent to the white carbon black is 5:1, stirring uniformly, and removing the solvent to obtain the solid anti-precipitation anti-aging agent B.
Example 3
The embodiment provides a preparation method of an anti-precipitation anti-aging agent, which comprises the following preparation steps:
the cardanol, the paraformaldehyde and the para-aminodiphenylamine are weighed according to the proportion of 1.25:1:0.95, then are added into a three-neck flask, and a proper amount of alcohol solution and petroleum ether solvent are measured by a measuring cylinder and added into the three-neck flask, so that raw materials are dissolved. Then the three-neck flask is placed in an oil bath pot, the temperature is set to be 30-140 ℃, the reaction is carried out for 1-24 hours, and the finished reaction liquid is black liquid.
Firstly, removing the solvent from the black reaction liquid to obtain the biological-based anti-aging agent solid. Weighing the bio-based anti-aging agent and the white carbon black in a ratio of 5:1, and fully grinding and uniformly mixing to obtain the solid anti-precipitation anti-aging agent C.
Example 4
The embodiment provides a preparation method of rubber, which comprises the following raw materials of 100 parts of natural rubber, 25 parts of calcium carbonate, 5 parts of zinc oxide, 1 part of stearic acid, 1 part of solid anti-precipitation anti-aging agent A, 2.5 parts of sulfur, 0.5 part of accelerator DM and 0.5 part of accelerator CZ. Mixing rubber raw materials, preparing unvulcanized rubber sheets by using a rubber processing mode commonly used in an open mill, and heating and pressurizing by using a flat vulcanizing machine to prepare vulcanized rubber.
Example 5
The embodiment provides a preparation method of rubber, which comprises the following raw materials of 100 parts of natural rubber, 25 parts of calcium carbonate, 5 parts of zinc oxide, 1 part of stearic acid, 1 part of solid anti-precipitation anti-aging agent B, 2.5 parts of sulfur, 0.5 part of accelerator DM and 0.5 part of accelerator CZ. Mixing rubber raw materials, preparing unvulcanized rubber sheets by using a rubber processing mode commonly used in an open mill, and heating and pressurizing by using a flat vulcanizing machine to prepare vulcanized rubber.
Example 6
The embodiment provides a preparation method of rubber, which comprises the following raw materials of 100 parts of natural rubber, 25 parts of calcium carbonate, 5 parts of zinc oxide, 1 part of stearic acid, 1 part of solid anti-precipitation anti-aging agent C, 2.5 parts of sulfur, 0.5 part of accelerator DM and 0.5 part of accelerator CZ. Mixing rubber raw materials, preparing unvulcanized rubber sheets by using a rubber processing mode commonly used in an open mill, and heating and pressurizing by using a flat vulcanizing machine to prepare vulcanized rubber.
Example 7
The embodiment provides a preparation method of an anti-precipitation anti-aging agent, which comprises the following preparation steps:
the cardanol, the paraformaldehyde and the para-aminodiphenylamine are weighed according to the proportion of 1:1:1, then are added into a three-neck flask, and a proper amount of alcohol solution and petroleum ether solvent are measured by a measuring cylinder and added into the three-neck flask, so that raw materials are dissolved. Then the three-neck flask is placed in an oil bath pot, the temperature is set to be 30-140 ℃, the reaction is carried out for 1-24 hours, and the finished reaction liquid is black liquid.
Removing the solvent of the black reaction liquid to obtain a bio-based anti-aging agent, adding an ethyl acetate volatile solvent to dissolve a bio-based anti-aging agent product, adding white carbon black while stirring successively, wherein the ratio of the bio-based anti-aging agent to the white carbon black is 5:1, and removing the solvent after stirring uniformly to obtain the solid anti-precipitation anti-aging agent.
Example 8
The embodiment provides a preparation method of an anti-precipitation anti-aging agent, which comprises the following preparation steps:
the cardanol, the paraformaldehyde and the para-aminodiphenylamine are weighed according to the proportion of 2:1:1, then are added into a three-neck flask, and a proper amount of alcohol solution and petroleum ether solvent are measured by a measuring cylinder and added into the three-neck flask, so that raw materials are dissolved. Then the three-neck flask is placed in an oil bath pot, the temperature is set to be 30-140 ℃, the reaction is carried out for 1-24 hours, and the finished reaction liquid is black liquid.
Removing the solvent of the black reaction liquid to obtain a bio-based anti-aging agent, adding an ethyl acetate volatile solvent to dissolve a bio-based anti-aging agent product, adding white carbon black while stirring successively, wherein the ratio of the bio-based anti-aging agent to the white carbon black is 5:1, and removing the solvent after stirring uniformly to obtain the solid anti-precipitation anti-aging agent.
Example 9
The embodiment provides a preparation method of an anti-precipitation anti-aging agent, which comprises the following preparation steps:
the cardanol, the paraformaldehyde and the para-aminodiphenylamine are weighed according to the proportion of 1.5:1:1, then added into a three-neck flask, and a proper amount of alcohol solution and petroleum ether solvent are measured by a measuring cylinder and added into the three-neck flask, so as to dissolve the raw materials. Then the three-neck flask is placed in an oil bath pot, the temperature is set to be 30-140 ℃, the reaction is carried out for 1-24 hours, and the finished reaction liquid is black liquid.
Removing the solvent of the black reaction liquid to obtain a bio-based anti-aging agent, adding an ethyl acetate volatile solvent to dissolve a bio-based anti-aging agent product, adding white carbon black while stirring successively, wherein the ratio of the bio-based anti-aging agent to the white carbon black is 1:1, and removing the solvent after stirring uniformly to obtain the solid anti-precipitation anti-aging agent.
Example 10
The embodiment provides a preparation method of an anti-precipitation anti-aging agent, which comprises the following preparation steps:
the cardanol, the paraformaldehyde and the para-aminodiphenylamine are weighed according to the proportion of 1.5:1:1, then added into a three-neck flask, and a proper amount of alcohol solution and petroleum ether solvent are measured by a measuring cylinder and added into the three-neck flask, so as to dissolve the raw materials. Then the three-neck flask is placed in an oil bath pot, the temperature is set to be 30-140 ℃, the reaction is carried out for 1-24 hours, and the finished reaction liquid is black liquid.
Removing the solvent of the black reaction liquid to obtain a bio-based anti-aging agent, adding an ethyl acetate volatile solvent to dissolve a bio-based anti-aging agent product, adding white carbon black while stirring successively, wherein the ratio of the bio-based anti-aging agent to the white carbon black is 10:1, and removing the solvent after stirring uniformly to obtain the solid anti-precipitation anti-aging agent.
Example 11
The cardanol, the paraformaldehyde and the para-aminodiphenylamine are weighed according to the proportion of 1.5:1:1, then added into a three-neck flask, and a proper amount of alcohol solution and petroleum ether solvent are measured by a measuring cylinder and added into the three-neck flask, so as to dissolve the raw materials. Then the three-neck flask is placed in an oil bath pot, the temperature is set to be 30-140 ℃, the reaction is carried out for 1-24 hours, and the finished reaction liquid is black liquid.
Removing the solvent of the black reaction liquid to obtain a bio-based anti-aging agent, adding an ethyl acetate volatile solvent to dissolve a bio-based anti-aging agent product, adding white carbon black while stirring successively, and removing the solvent after stirring uniformly to obtain the solid anti-precipitation anti-aging agent, wherein the ratio of the bio-based anti-aging agent to the white carbon black is 0.1:1.
Comparative example 1
The comparative example provides a preparation method of rubber, which comprises the following raw materials of 100 parts of natural rubber, 25 parts of calcium carbonate, 5 parts of zinc oxide, 1 part of stearic acid, 2.5 parts of sulfur, 0.5 part of accelerator DM and 0.5 part of accelerator CZ. Mixing rubber raw materials, preparing unvulcanized rubber sheets by using a rubber processing mode commonly used in an open mill, and heating and pressurizing by using a flat vulcanizing machine to prepare vulcanized rubber.
Comparative example 2
The comparative example provides a preparation method of rubber, which comprises the following raw materials of 100 parts of natural rubber, 25 parts of calcium carbonate, 5 parts of zinc oxide, 1 part of stearic acid, 0 part of anti-aging agent 4010, 2.5 parts of sulfur, 0.5 part of accelerator DM and 0.5 part of accelerator CZ. Mixing rubber raw materials, preparing unvulcanized rubber sheets by using a rubber processing mode commonly used in an open mill, and heating and pressurizing by using a flat vulcanizing machine to prepare vulcanized rubber.
Comparative example 3
The comparative example provides a preparation method of rubber, which comprises the following raw materials of 100 parts of natural rubber, 25 parts of calcium carbonate, 5 parts of zinc oxide, 1 part of stearic acid, 1 part of cardanol, 2.5 parts of sulfur, 0.5 part of accelerator DM and 0.5 part of accelerator CZ. Mixing rubber raw materials, preparing unvulcanized rubber sheets by using a rubber processing mode commonly used in an open mill, and heating and pressurizing by using a flat vulcanizing machine to prepare vulcanized rubber.
After the rubber cut pieces prepared in examples 4 to 6 and comparative examples 2 to 3 were subjected to extraction experiments in methanol and toluene, respectively, the rubber cut pieces were immersed in a solvent at room temperature for 24 hours, and after the extraction was completed, the solvent was removed by heating in a vacuum oven, and the Initial Oxidation Temperature (IOT) test of the vulcanized rubber after the advance of the extraction was performed. The using device comprises: a differential scanning calorimeter; the testing method comprises the following steps: the test gas atmosphere is switched to be air, the temperature is kept at 25 ℃ for 5 minutes, and then the temperature is increased at 10 ℃ per minute until the oxidation exothermic peak value appears, and the experiment is stopped. The test results obtained are shown in table 1 below:
TABLE 1
| Comparative example 2 | Comparative example 3 | Example 2 | Example 3 | Example 4 | ||
| Toluene (toluene) | IOT reduction value delta T/DEGC after pumping advance | 16.1 | 10.2 | 3.5 | 4.1 | 4.7 |
| Methanol | IOT reduction value delta T/DEGC after pumping advance | 3.0 | 2.1 | 0.2 | 0.4 | 0.8 |
As is clear from Table 1 above, the rubber of the examples was reduced in the initial oxidation temperature after extraction in polar (methanol) and nonpolar (toluene) solvents by the large particle fixation of white carbon black and the co-crosslinking of cardanol-aromatic amine complex antioxidant, both of which were smaller than those of the comparative examples.
The thermal oxidative aging test was performed on the rubber sheets of examples 5 and 6 and comparative examples 1 to 3, the change of the tensile strength of the rubber sheets at different times of thermal oxidative aging is shown in fig. 1, and it is known from examples 5 and 6 that the tensile strength of example 5 is optimal in the thermal oxidative aging resistance, the stability of the modified cardanol and the white carbon black compounded by the solvent method in the rubber is obviously superior to that of the solid anti-precipitation anti-aging agent compounded by the grinding method, and the performances of example 6 and comparative example 2 are similar, and are superior to those of the thermal oxidative resistance of comparative examples 1 and 3.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. The preparation method of the anti-precipitation anti-aging agent is characterized by comprising the following steps of: and (3) dissolving cardanol, paraformaldehyde and para-aminodiphenylamine in a solvent according to a certain proportion, heating and reacting to obtain a black reaction solution containing modified cardanol, uniformly mixing the modified cardanol with a solid carrier, and compounding to obtain the anti-precipitation anti-aging agent.
2. The method for preparing an anti-precipitation anti-aging agent according to claim 1, wherein the mass ratio of cardanol, paraformaldehyde and p-aminodiphenylamine is 1-2:1:0.9-1.05.
3. The method for preparing an anti-precipitation anti-aging agent according to claim 1, wherein the heating reaction temperature is 30-140 ℃ and the reaction time is 1-24 hours.
4. The method for producing an anti-aging agent according to claim 1, wherein the solid support is white carbon black.
5. The method for preparing an anti-aging agent according to claim 1, wherein the specific step of compounding the modified cardanol with a solid carrier comprises: adding a solid load into the black reaction liquid containing the modified cardanol, stirring and mixing uniformly, and removing the solvent to obtain the solid anti-precipitation anti-aging agent.
6. The method for preparing an anti-aging agent according to claim 1, wherein the specific step of compounding the modified cardanol with a solid carrier comprises: removing the solvent from the black reaction solution containing the modified cardanol to obtain the modified cardanol, dissolving the modified cardanol in a volatile solvent, adding a solid load, stirring and mixing uniformly, and removing the volatile solvent to obtain the solid anti-precipitation anti-aging agent.
7. The method for preparing an anti-aging agent according to claim 1, wherein the specific step of compounding the modified cardanol with a solid carrier comprises: removing the solvent from the black reaction solution containing the modified cardanol to obtain the modified cardanol, mixing the modified cardanol with a solid carrier, and sufficiently grinding to obtain the solid anti-precipitation anti-aging agent.
8. The process for producing an anti-aging agent according to any one of claims 5 to 7, wherein the mass ratio of the modified cardanol to the solid load is 0.1 to 10:1.
9. An anti-aging agent for precipitation obtained by the production process according to claim 1.
10. The anti-precipitation anti-aging agent according to claim 9, wherein the anti-precipitation anti-aging agent is applied to rubber.
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