CN112824459A - White carbon black modification method, rubber composite material, preparation method and application thereof - Google Patents
White carbon black modification method, rubber composite material, preparation method and application thereof Download PDFInfo
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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Abstract
The invention discloses a modification method of white carbon black, a rubber composite material, a preparation method and application thereof, wherein the modification method comprises the steps of dissolving dopamine in an organic solvent, adding white carbon black and cerium salt for catalytic reaction, and filtering, washing and drying a product after the reaction is finished to obtain the dopamine modified white carbon black; the rubber composite material comprises 5-10 parts by weight of the dopamine modified white carbon black, and 100 parts by weight of latex and/or raw rubber with the dry rubber content of 50-60 wt%; the rubber composite material can be used in tires, latex sheets and latex sponges. The modified white carbon black is used as a rubber auxiliary agent, so that a rubber product has excellent tensile property and rebound resilience, excellent aging resistance and longer service life.
Description
Technical Field
The invention relates to the technical field of rubber modification, in particular to a modification method of white carbon black, a rubber composite material, a preparation method and application thereof.
Background
The white carbon black is a general term for white powdery X-ray amorphous silicic acid and silicate products, mainly refers to precipitated silica, fumed silica and superfine silica gel, and the components of the white carbon black can be SiO2·nH2O represents, wherein nH2O is present in the form of surface hydroxyl groups. White carbon black is a reinforcing filling modification material with high specific surface area, high structure and high activity, has no pollution to transparent products and light-colored products, has better reinforcing effect on natural latex, is an ideal reinforcing agent of the natural latex, takes gas-phase white carbon black as an example, has the reinforcing principle that the white carbon black is widely applied to room-temperature vulcanized silicone rubber and high-temperature vulcanized silicone rubber, is dispersed in a matrix in the form of agglomerates to form a two-dimensional network longitudinal structure, increases the contact surface with a silicone rubber base material, and further increases cross-linking points formed in the vulcanization process, thereby playing roles of withering and reinforcing the silicone rubber. And the three-dimensional network longitudinal structure formed by the fumed silica only has relative stability, can be temporarily damaged under the action of external force, so that the viscosity of the system is reduced, and the system has good fluidity.
However, the white carbon black used as the rubber additive is easy to agglomerate in the emulsion state, so that the bonding force between the white carbon black and the rubber matrix is poor, most white carbon black particles cannot directly contact with latex particles, and the bonding effect between the white carbon black and the latex particles is reduced, so that the reinforcing effect cannot be achieved, and the performance of the adhesive film is reduced. In order to solve this problem, some researchers have modified the polymer coating of white carbon black, for example, by using dopamine monomer as raw material and performing "auto-oxidative polymerization" in an aqueous solution of weak alkaline buffer, to generate poly-dopamine adhered on the surface of white carbon black. Therefore, the acting force between hydroxyl groups on the surface of the white carbon black is reduced by introducing the poly-dopamine layer, the surface structure of the white carbon black is changed, and the problem of easy agglomeration of the nano white carbon black is solved. However, the modified white carbon black serving as the rubber additive cannot solve the problems of insufficient aging resistance and easy aging when the natural rubber dairy product is in large-area contact with air, and the problems that the natural rubber latex product is aged and the service life of the product is shortened due to the fact that some variable-valence metal ions also can be solved.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a modification method of white carbon black, a rubber composite material, a preparation method and application thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
a modification method of white carbon black comprises the following steps:
dissolving dopamine in a polar solvent, adding white carbon black and cerium salt to perform coupling reaction, and filtering, washing and drying a product after the reaction is finished to obtain the dopamine modified white carbon black.
The dopamine is called 3, 4-dihydroxy phenethylamine and has the structure
The method utilizes the hydroxyl on the surface of the white carbon black and the hydroxyl of dopamine to generate the dopamine modified white carbon black through the coupling reaction under the catalysis of cerium ions. The reaction mechanism is shown in figures 1-3:
in the reaction, a polar solvent without active hydrogen elements is selected as a reaction solvent of dopamine and white carbon black, and cerium salt is selected as a catalyst, wherein the dopamine, the white carbon black and the cerium salt coexist in the reaction solvent, and the cerium salt can catalyze hydroxyl to form free radicals during the reaction, so that the dopamine and silicon dioxide are covalently bonded to react. The polar solvent without active hydrogen elements has lower hydrogen atom activity than that of water and alcohols, so that the stable existence of free radicals formed by catalysis of cerium salt can be ensured, the utilization rate of active sites after catalysis is further improved, and the dopamine modified white carbon black obtained by catalytic reaction of dopamine and white carbon black through cerium salt contains a large amount of phenolic hydroxyl groups with free radical capture activity, so that the aims of obviously inhibiting the generation of chain free radicals in the thermal oxidation aging process of natural latex and improving the aging performance of latex products can be fulfilled. Secondly, after the dopamine modified white carbon black is added into the natural latex, the dopamine modified white carbon black has a supporting effect on foam pores of the natural latex sponge, plays a certain buffering effect, enables the compression permanent deformation to be small, has good buffering resilience, enhances the mechanical property of the natural latex sponge, enables the product to have excellent tensile property and resilience, and meanwhile can improve the aging resistance of the natural latex sponge and prolong the service life.
In one embodiment, the dopamine modified white carbon black comprises the following components in parts by weight:
100 parts of white carbon black, 5-20 parts of dopamine and 1-10 parts of cerium salt.
In one embodiment, the reaction temperature of the catalytic reaction is 50 ℃ to 70 ℃ and the reaction time is 3 to 10 hours. Under the reaction condition, the catalytic activity of the cerium salt is the largest, and dopamine can fully react with the white carbon black to generate the dopamine modified white carbon black.
In this embodiment, the reaction temperature is set to 50 ℃ to 70 ℃, preferably 60 ℃, because the inventor finds that when the cerium salt catalyzes the macromolecule such as starch, the temperature is only about 40 ℃ to 45 ℃, but the temperature of 40 ℃ to 45 ℃ is not suitable for catalyzing silica, because the hydroxyl activity of silica is relatively low, the catalyst can react only by adding strong acid and strong base, and the catalytic effect of the catalyst on the hydroxyl on silica is increased after the temperature is raised, but if the temperature is too high, the reactant dopamine is polymerized, and the polymerized dopamine has anti-aging performance but has slightly poor performance compared with small dopamine molecules.
In one embodiment, the polar solvent is dimethylformamide or dimethylsulfoxide.
Dimethylformamide (DMF) is a transparent liquid, miscible with water and most organic solvents. Dimethylformamide is a polar (hydrophilic) aprotic solvent with a high boiling point and promotes the progress of the SN2 reaction mechanism. Molecular formula C3H7NO, molecular weight 73.10, relative density 0.9445(25 ℃), melting point-61 ℃, boiling point 152.8 ℃ and flash point 57.78 ℃. The vapor density is 2.51, the vapor pressure is 0.49kpa (3.7mmHg 25 ℃), and the self-ignition point is 445 ℃. Refractive index 1.42817, solubility parameter δ 12.1. The dimethyl formamide is selected because the dimethyl formamide has larger polarity, the activity of hydrogen atoms of the dimethyl formamide is lower than that of water and alcohols, and free radicals generated by catalysis of cerium salt of reactants can stably exist, so that the utilization rate of the catalytic active sites is improved.
In one embodiment, the cerium salt is a tetravalent cerium salt, such as one or more of ammonium nitrate, cerium sulfate, and cerium oxide.
A rubber composite material comprises 5-10 parts by weight of the dopamine modified white carbon black, and 100 parts by weight of latex and/or raw rubber with the dry rubber content of 50-60 wt%.
The rubber composite material is applied to tires, latex sheets and latex sponges.
In one embodiment, the latex foam is a latex foam mattress, a latex foam pillow, a latex foam cushion, or a latex foam automobile cushion.
In one embodiment, the preparation method of the latex sponge comprises the following steps: and dispersing the dopamine modified white carbon black into a base material by taking natural latex as the base material according to the weight part, and sequentially carrying out foaming, injection molding, gelling, vulcanizing, demolding, washing and drying to obtain the latex sponge product.
Natural rubber latex is a natural polymer product derived from hevea brasiliensis. The natural latex has excellent comprehensive properties of good film forming property, high wet gel strength, easy vulcanization, high product strength, large elongation, good wear resistance, small creep deformation and the like. Is widely applied to various fields of industry, agriculture, national defense, traffic, medical treatment and health, and the like. The sponge product prepared from the natural latex has the advantages of light weight, large volume, environmental protection, excellent buffering performance, high elasticity, special comfortable touch feeling, quick recovery after deformation, creep resistance and permanent deformation resistance, excellent buffering and pressure reducing performance, compression fatigue resistance and the like.
Compared with the prior art, the invention has the following beneficial effects:
drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows that hydroxyl on the surface of white carbon black is catalyzed by cerium ions to form free radicals;
FIG. 2 shows that hydroxyl groups of dopamine are catalyzed by cerium ions to form radicals;
FIG. 3 shows the coupling reaction of white carbon black and dopamine under the catalysis of cerium ions.
Detailed Description
In order to better understand the present invention, the present invention is further illustrated by examples, but the scope of the present invention is not limited to the examples. Unless otherwise specified, 1 part in the following examples refers to 1 g. In the following examples, white carbon black is provided by Jiangxi Brightness chemical Co., Ltd; natural latex is supplied by Hainan rubber group, Inc., and cerium salt is supplied by Shanghai Arlatin Biochemical Co., Ltd; dimethylformamide is available from the national pharmaceutical group chemical agents limited.
Example 1
The invention provides a latex sponge compounded by modified white carbon black and raw rubber, which is prepared by the following steps:
(1) preparation of dopamine modified white carbon black anti-aging agent
Drying white carbon black in a forced air drying oven at 100 ℃ to remove water, dissolving 5 parts of dopamine in dimethylformamide, adding 100 parts of white carbon black and 1 part of cerium nitrate, carrying out catalytic reaction for 3 hours at the temperature of 50 ℃, and filtering, washing and drying a product after the reaction is finished to obtain dopamine modified white carbon black;
(2) preparation of latex sponge composite
Preparing sulphur, an accelerator ZDC, zinc oxide, sodium fluosilicate and the dopamine modified white carbon black obtained in the step (1) into a dispersion by using deionized water respectively, wherein the dispersion comprises 5 parts of dopamine modified white carbon black, 1 part of a foaming agent, 2.5 parts of sulphur, 1 part of an accelerator ZDC (zinc diethyldithiocarbamate), 2 parts of zinc oxide, 1 part of sodium silicofluoride and 0.1 part of potassium hydroxide;
taking 100 parts by weight of natural latex with the dry rubber content of 50 wt% as a base material, adding 0.1 part of potassium hydroxide with the concentration of 10%, reducing the ammonia content in the latex to 0.25% by mechanical stirring, adding a foaming agent, dopamine modified white carbon black, sulfur, an accelerator ZDC and other dispersions into the mixed latex, and curing to obtain the rubber composite material;
(3) synthetic latex sponge
And (3) foaming the rubber composite material obtained in the step (2) to a certain multiple by matching with latex through a foaming machine, adding a dispersion of zinc oxide and sodium fluosilicate, and then performing injection molding, gelling and shaping, vulcanization, demolding, washing and drying to obtain a finished product.
Example 2
The invention provides a latex sponge compounded by modified white carbon black and natural latex, which is prepared by the following steps:
(1) preparation of dopamine modified white carbon black anti-aging agent
Drying white carbon black in a vacuum drying oven at 110 ℃ to remove water, dissolving 13 parts of dopamine in dimethylformamide, adding 100 parts of white carbon black and 5 parts of cerium sulfate, carrying out catalytic reaction at 60 ℃ for 6 hours, and filtering, washing and drying a product after the reaction is finished to obtain dopamine modified white carbon black;
(2) preparation of rubber composite Material
Preparing sulfur, an accelerator ZDC, zinc oxide, sodium fluosilicate and the dopamine modified white carbon black obtained in the step (1) into dispersions by using deionized water respectively, wherein the dispersions comprise 8 parts of dopamine modified white carbon black, 1 part of a foaming agent, 2.5 parts of sulfur, 1 part of an accelerator ZDC (zinc diethyldithiocarbamate), 2 parts of zinc oxide, 1 part of sodium silicofluoride and 0.1 part of potassium hydroxide;
taking 100 parts by weight of natural latex with the dry rubber content of 55 wt% as a base material, adding 0.1 part of potassium hydroxide with the concentration of 10%, reducing the ammonia content in the latex to 0.25% by mechanical stirring, adding a foaming agent, dopamine modified white carbon black, sulfur, an accelerator ZDC and other dispersions into the mixed latex, and curing to obtain the rubber composite material;
(3) synthetic latex sponge
And (3) foaming the rubber composite material obtained in the step (2) to a certain multiple by matching with latex through a foaming machine, adding a dispersion of zinc oxide and sodium fluosilicate, and then performing injection molding, gelling and shaping, vulcanization, demolding, washing and drying to obtain a finished product.
Example 3
The invention provides a latex sheet compounded by modified white carbon black and natural latex, and the preparation method comprises the following steps:
(1) preparation of dopamine modified white carbon black anti-aging agent
Drying white carbon black in a vacuum drying oven at 100 ℃ to remove water, dissolving 20 parts of dopamine in dimethylformamide, adding 100 parts of white carbon black and 10 parts of cerium oxide, carrying out catalytic reaction for 10 hours at 70 ℃, and filtering, washing and drying a product after the reaction is finished to obtain dopamine modified white carbon black;
(2) preparation of rubber composite Material
Preparing sulfur, an accelerator ZDC, zinc oxide, sodium fluosilicate and the dopamine modified white carbon black obtained in the step (1) into dispersions by using deionized water respectively, wherein the dispersions comprise 10 parts of dopamine modified white carbon black, 1 part of a foaming agent, 2.5 parts of sulfur, 1 part of an accelerator ZDC (zinc diethyldithiocarbamate), 2 parts of zinc oxide, 1 part of sodium silicofluoride and 0.1 part of potassium hydroxide;
taking 100 parts by weight of natural latex with the dry rubber content of 60 wt% as a base material, adding 0.1 part of potassium hydroxide with the concentration of 10%, reducing the ammonia content in the latex to 0.25% by mechanical stirring, adding a foaming agent, dopamine modified white carbon black, sulfur, an accelerator ZDC and other dispersions into the mixed latex, and curing to obtain the rubber composite material;
(3) synthetic latex sheet
And (3) foaming the rubber composite material obtained in the step (2) to a certain multiple by matching with latex through a foaming machine, adding a dispersion of zinc oxide and sodium fluosilicate, and then performing injection molding, gelling and shaping, vulcanization, demolding, washing and drying to obtain a finished product.
Example 4
The invention provides a latex sponge compounded by modified white carbon black and natural latex, which is prepared by the following steps:
(1) preparation of dopamine modified white carbon black anti-aging agent
Drying white carbon black in a vacuum drying oven at 100 ℃ to remove water, dissolving dopamine in dimethylformamide, adding dried white carbon black and ceric nitrate, reacting at 50 ℃ for 8 hours, and filtering, washing and drying a product after the reaction is finished to obtain the dopamine modified white carbon black; wherein the mass ratio of the white carbon black to the dopamine is 100:8, and the dosage of the ceric nitrate amine is 1 percent of the mass of the white carbon black;
(2) preparation of rubber composite Material
Preparing sulphur, an accelerator ZDC, zinc oxide, sodium fluosilicate and the dopamine modified white carbon black obtained in the step (1) into a dispersion by using deionized water respectively, wherein the dispersion comprises 5 parts of dopamine modified white carbon black, 1 part of a foaming agent, 2.5 parts of sulphur, 1 part of an accelerator ZDC (zinc diethyldithiocarbamate), 2 parts of zinc oxide, 1 part of sodium silicofluoride and 0.1 part of potassium hydroxide;
taking 100 parts of concentrated natural latex with the dry rubber content of 60%, adding 0.1 part of potassium hydroxide with the concentration of 10%, reducing the ammonia content of the latex to 0.25% by mechanical stirring, adding foaming agent, dopamine modified white carbon black, sulfur, accelerator ZDC and other dispersions into the mixed latex, and curing to obtain the rubber composite material;
(3) synthetic latex sponge
And (3) foaming the rubber composite material obtained in the step (2) to a certain multiple by matching with latex through a foaming machine, adding a dispersion of zinc oxide and sodium fluosilicate, and then performing injection molding, gelling and shaping, vulcanization, demolding, washing and drying to obtain a finished product.
Example 5
The invention provides a latex sponge compounded by modified white carbon black and natural latex, which is prepared by the following steps:
(1) preparation of dopamine modified white carbon black anti-aging agent
Drying white carbon black in a vacuum drying oven at 110 ℃ to remove water, dissolving dopamine in dimethylformamide, adding dried white carbon black and ceric ammonium nitrate, reacting at 60 ℃ for 4 hours, and filtering, washing and drying a product after the reaction is finished to obtain the dopamine modified white carbon black; wherein the mass ratio of the white carbon black to the dopamine is 100:10, and the dosage of the ceric nitrate amine is 2 percent of the mass of the white carbon black;
(2) preparation of rubber composite Material
Preparing sulfur, an accelerator ZDC, zinc oxide, sodium fluosilicate and the dopamine modified white carbon black obtained in the step (1) into dispersions by using deionized water respectively, wherein the dispersions comprise 8 parts of dopamine modified white carbon black, 1.5 parts of a foaming agent, 2.5 parts of sulfur, 1 part of an accelerator ZDC (zinc diethyldithiocarbamate), 2 parts of zinc oxide, 1 part of sodium silicofluoride and 0.1 part of potassium hydroxide;
taking 100 parts of concentrated natural latex with the dry rubber content of 60%, adding 0.1 part of potassium hydroxide with the concentration of 10%, reducing the ammonia content of the latex to 0.25% by mechanical stirring, adding foaming agent, dopamine modified white carbon black, sulfur, accelerator ZDC and other dispersions into the mixed latex, and curing to obtain the rubber composite material;
(3) synthetic latex sponge
And (3) foaming the rubber composite material obtained in the step (2) to a certain multiple by matching with latex through a foaming machine, adding a dispersion of zinc oxide and sodium fluosilicate, and then performing injection molding, gelling and shaping, vulcanization, demolding, washing and drying to obtain a finished product.
Example 6
The invention provides a latex sponge compounded by modified white carbon black and natural latex, which is prepared by the following steps:
(1) preparation of dopamine modified white carbon black anti-aging agent
Drying white carbon black in a forced air drying oven at 100 ℃ to remove water, dissolving dopamine in dimethylformamide, adding dried white carbon black and ceric ammonium nitrate, reacting at 70 ℃ for 3 hours, and filtering, washing and drying a product after the reaction is finished to obtain the dopamine modified white carbon black; wherein the mass ratio of the white carbon black to the dopamine is 100:12, and the dosage of the ceric nitrate amine is 3 percent of the mass of the white carbon black;
(2) preparation of rubber composite Material
Preparing sulfur, an accelerator ZDC, zinc oxide, sodium fluosilicate and the dopamine modified white carbon black obtained in the step (1) into dispersions by using deionized water respectively, wherein the dispersions comprise 10 parts of dopamine modified white carbon black, 2 parts of a foaming agent, 2.5 parts of sulfur, 1 part of an accelerator ZDC (zinc diethyldithiocarbamate), 2 parts of zinc oxide, 1 part of sodium silicofluoride and 0.1 part of potassium hydroxide;
taking 100 parts of concentrated natural latex with the dry rubber content of 60%, adding 0.1 part of potassium hydroxide with the concentration of 10%, reducing the ammonia content of the latex to 0.25% by mechanical stirring, adding foaming agent, dopamine modified white carbon black, sulfur, accelerator ZDC and other dispersions into the mixed latex, and curing to obtain the rubber composite material;
(3) synthetic latex sponge
And (3) foaming the rubber composite material obtained in the step (2) to a certain multiple by matching with latex through a foaming machine, adding a dispersion of zinc oxide and sodium fluosilicate, and then performing injection molding, gelling and shaping, vulcanization, demolding, washing and drying to obtain a finished product.
Comparative example
Preparing a commercial antioxidant 246 (purchased from Shijiazhuang Baina chemical auxiliary agent Co., Ltd.), sulfur, an accelerator ZDC, zinc oxide and sodium fluosilicate into dispersions by respectively using deionized water, wherein the distribution ratio of the components is the same as that in example 4 except that the commercial antioxidant 246 is used for replacing dopamine modified white carbon black;
taking 100 parts of concentrated natural latex with the dry rubber content of 60%, adding 0.1 part of potassium hydroxide with the concentration of 10%, reducing the ammonia content of the latex to 0.25% by mechanical stirring, adding foaming agent and dispersion such as dopamine modified white carbon black, sulfur and accelerator ZDC prepared by the method into the mixed latex, curing for a period of time, foaming the matched latex to a certain multiple by a foaming machine, adding dispersion such as zinc oxide and sodium fluosilicate, injecting into a model, shaping, vulcanizing, demolding, washing with water and drying to obtain a finished product.
The following performance tests and analyses were performed on the products obtained in examples 4 to 6 of the present invention and comparative examples, and the detection indexes and methods were as follows:
apparent density: the apparent density of the foam and the rubber was measured according to GB/T6343-2009.
The rebound resilience: the rebound rate of the sponge sample is measured according to the measurement of the elasticity of the GB/T10652-2001 high polymer porous elastic material.
Compression set: the compression set of the porous elastomeric material of the high polymer is measured according to GB/T10653-2001. Tensile strength and elongation at break: the tensile strength and elongation at break of the flexible foams were determined in accordance with GB/T6344-2008 on an electronic tensile tester. The moving speed of the clamp of the tensile testing machine is 500mm/min +/-50 mm/min. Hot air ageing tests ageing was carried out in an ageing test cabinet according to GB/T3512-2001.
The results are shown in the following table:
table 1 comparative table of property characterization
As can be seen from Table 1, the rebound rate, tensile strength and elongation at break of the products obtained in the examples 4-6 are far greater than those of the comparative example before and after aging, and the compression set is far less than that of the comparative example, so that the modified white carbon black provided by the application is used as a rubber additive, and not only can the rubber product have excellent tensile resistance and rebound resilience, but also the rubber product has excellent aging resistance.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (9)
1. The method for modifying white carbon black is characterized by comprising the following steps:
dissolving dopamine in a polar solvent, adding white carbon black and cerium salt to perform coupling reaction, and filtering, washing and drying a product after the reaction is finished to obtain the dopamine modified white carbon black.
2. The method according to claim 1, wherein the dopamine modified white carbon black comprises the following components in parts by weight:
100 parts of white carbon black, 5-20 parts of dopamine and 1-10 parts of cerium salt.
3. The method of claim 1, wherein the catalytic reaction is carried out at a temperature of 50 ℃ to 70 ℃ for a time of 3 to 10 hours.
4. The method of claim 1, wherein the polar solvent is dimethylformamide or dimethylsulfoxide.
5. The method according to claim 1, wherein the cerium salt is one or more of ammonium nitrate, cerium sulfate and cerium oxide.
6. A rubber composite material, characterized by comprising 5-10 parts by weight of the dopamine modified white carbon black according to any one of claims 1 to 5, and 100 parts by weight of latex and/or raw rubber with a dry rubber content of 50-60 wt%.
7. The rubber composite of claim 6, wherein the rubber composite is used in tires, latex sheets, and latex sponges.
8. The rubber composite of claim 7, wherein the latex foam is a latex foam mattress, a latex foam pillow, a latex foam cushion, or a latex foam automotive cushion.
9. The rubber composite according to claim 7 or 8, wherein the latex sponge is prepared by a method comprising: and dispersing the dopamine modified white carbon black into a base material by taking natural latex as the base material according to the weight part, and sequentially carrying out foaming, injection molding, gelling, vulcanizing, demolding, washing and drying to obtain the latex sponge product.
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| CN104650420A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Preparation method of rubber composition containing modified white carbon black |
| CN105390642A (en) * | 2015-11-06 | 2016-03-09 | 中国第一汽车股份有限公司 | Preparation method for poly-dopamine modified ceramic particle nonwoven diaphragm |
| CN106750462A (en) * | 2016-12-19 | 2017-05-31 | 大连理工大学 | A kind of surface modifying method of dopamine and its derivative polymerization and crosslinking curing |
| US20170306108A1 (en) * | 2015-07-15 | 2017-10-26 | Cabot Corporation | Methods of making an elastomer composite reinforced with silica and carbon black and products containing same |
| CN109517234A (en) * | 2018-10-31 | 2019-03-26 | 安徽春辉仪表线缆集团有限公司 | A kind of ageing-resistant nitile-butadiene rubber composite material of instrument and meter sealing ring |
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| US20140193489A1 (en) * | 2013-01-07 | 2014-07-10 | Bar-Ilan University | Dopamine Nanocapsules and Uses Thereof |
| CN104650420A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Preparation method of rubber composition containing modified white carbon black |
| US20170306108A1 (en) * | 2015-07-15 | 2017-10-26 | Cabot Corporation | Methods of making an elastomer composite reinforced with silica and carbon black and products containing same |
| CN105390642A (en) * | 2015-11-06 | 2016-03-09 | 中国第一汽车股份有限公司 | Preparation method for poly-dopamine modified ceramic particle nonwoven diaphragm |
| CN106750462A (en) * | 2016-12-19 | 2017-05-31 | 大连理工大学 | A kind of surface modifying method of dopamine and its derivative polymerization and crosslinking curing |
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