CN114437430B - High-wear-resistance rubber-based composite material and preparation method thereof - Google Patents

High-wear-resistance rubber-based composite material and preparation method thereof Download PDF

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CN114437430B
CN114437430B CN202210183380.1A CN202210183380A CN114437430B CN 114437430 B CN114437430 B CN 114437430B CN 202210183380 A CN202210183380 A CN 202210183380A CN 114437430 B CN114437430 B CN 114437430B
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ionic liquid
rubber
aramid
ethanol solution
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CN114437430A (en
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李卓
张瑞
苑欣娜
张百慧
刘桂志
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Qingdao University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C08L15/005—Hydrogenated nitrile rubber
    • 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
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Health & Medical Sciences (AREA)
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Abstract

The invention discloses a high-wear-resistance rubber-based composite material and a preparation method thereof, and belongs to the field of high-polymer composite materials. The composite material provided by the invention comprises the following raw materials in parts by weight: 100 parts of rubber, 2-12 parts of active agent, 0.5-2 parts of anti-aging agent, 20-70 parts of carbon black, 1-20 parts of plasticizer, 0.5-2 parts of vulcanizing agent, 0.5-2 parts of accelerator and 1-50 parts of aramid fiber treated by ionic liquid ethanol solution. As the ionic liquid is used for treatment between the aramid fiber and the rubber base in the high-wear-resistance rubber-based composite material, the adhesiveness is obviously improved, and the tear resistance and wear resistance of the composite material are obviously improved.

Description

High-wear-resistance rubber-based composite material and preparation method thereof
Technical Field
The invention relates to the technical field of polymer composite materials, in particular to a bonding method of a high-wear-resistance rubber-based composite material.
Background
With the development of rubber industry technology, higher and higher requirements are placed on the properties of rubber materials. The introduction of high performance fibers, such as aramid fibers, into rubber matrix to make composite materials has become one of the hot spots of research and application. At present, the aramid fiber/rubber composite material is widely applied to the fields of tires, conveyor belts, sealing elements, wipers and the like. These products all put high demands on the mechanical properties and tribological properties of the materials. The product has better mechanical/tribological performance and has important significance for prolonging the service life of the product, ensuring the safety of the product, reducing the energy consumption and the like. However, there are also certain problems with aramid/rubber composites in the manufacturing process. The fibers do not achieve chemical bonding with the rubber matrix, and when the fibers are applied in the form of pulp, they are difficult to disperse in the rubber matrix. Both of these problems can lead to reduced composite properties. To solve this problem, a series of methods such as pre-dispersion, surface modification, etc. have been used so far to improve the dispersibility of AP in a rubber matrix. However, these methods tend to be compatible with the properties of the composite material, such as stretch, tear, abrasion resistance, etc.
Therefore, a new method is needed to improve the mechanical properties and wear resistance of the composite material.
Disclosure of Invention
In order to meet the purpose of preparing the rubber-based composite material with good comprehensive performance and excellent wear resistance, the invention provides the following technical scheme:
the invention provides a high-wear-resistance rubber-based composite material which is characterized by comprising the following raw materials in parts by weight: 100 parts of rubber, 2-12 parts of active agent, 0.5-2 parts of anti-aging agent, 20-70 parts of carbon black, 1-20 parts of plasticizer, 0.5-2 parts of vulcanizing agent, 0.5-2 parts of accelerator and 1-50 parts of aramid fiber treated by ionic liquid ethanol solution.
Preferably, the rubber comprises: nitrile rubber, hydrogenated nitrile rubber, natural rubber, styrene butadiene rubber and neoprene rubber.
Preferably, the active agent comprises 1.5-8 parts of zinc oxide and 0.5-4 parts of stearic acid;
the anti-aging agent comprises a 2, 4-trimethyl-1, 2-dihydroquinoline polymer, N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine and N-phenyl-2-naphthylamine;
the carbon black includes N660, N550, N330, and N339;
the plasticizer comprises dioctyl phthalate, pine tar and aromatic hydrocarbon oil;
the accelerator comprises N-cyclohexyl-2-benzothiazole sulfenamide, tetramethylthiuram disulfide, N-dicyclohexyl-2-benzothiazole sulfenamide, hexamethylenetetramine, N-tertiary butyl-2-benzothiazole sulfenamide, tetrabenzyl thiuram disulfide and dibenzothiazyl disulfide;
the vulcanizing agent comprises insoluble sulfur and common sulfur powder;
preferably, the aramid comprises chopped aramid and aramid pulp, and the aspect ratio of the chopped aramid is 80-500.
Preferably, the method for treating the aramid fibers by the ionic liquid comprises the following steps:
(1) Adding the ionic liquid into ethanol, and fully dissolving to obtain ionic liquid ethanol solution;
(2) Immersing aramid fiber into the ionic liquid ethanol solution for immersing;
(3) And drying the soaked aramid fiber.
Preferably, the ionic liquid comprises cations and anions having a carbon-carbon double bond structure in a side chain; the concentration of the ionic liquid ethanol solution is 0.05-2g/L; the mass ratio of the ionic liquid to the aramid fiber in the ionic liquid ethanol solution is 1:30-1:300; the temperature of the drying is 60-150 ℃.
Preferably, the cation having a carbon-carbon double bond structure in the side chain includes the following structure:
preferably, the preparation method of the composite material comprises the following steps:
(1) Mixing rubber, an active agent, an anti-aging agent, carbon black, a plasticizer and aramid fibers treated by ionic liquid ethanol solution in an internal mixer for 5-10min at 60-120 ℃ as an initial temperature to obtain a primary product;
(2) Adding an accelerator and a vulcanizing agent into the primary product, mixing for 5-15min in an open mill at the initial temperature of 20-40 ℃ and uniformly mixing to obtain a semi-finished product;
(3) And (3) placing the semi-finished product into a mould for vulcanization to obtain the high-wear-resistance rubber-based composite material, wherein the vulcanization temperature is 140-170 ℃ and the vulcanization time is 10-20min.
Secondly, the invention provides a preparation method of the high wear-resistant rubber-based composite material, which is characterized by comprising the following steps:
(1) Mixing rubber, an active agent, an anti-aging agent, carbon black, a plasticizer and aramid fibers treated by ionic liquid ethanol solution in an internal mixer for 5-10min at 60-120 ℃ as an initial temperature to obtain a primary product;
(2) Adding an accelerator and a vulcanizing agent into the primary product, mixing for 5-15min in an open mill at the initial temperature of 20-40 ℃ and uniformly mixing to obtain a semi-finished product;
(3) And (3) placing the semi-finished product into a mould for vulcanization to obtain the high-wear-resistance rubber-based composite material, wherein the vulcanization temperature is 140-170 ℃ and the vulcanization time is 10-20min.
Preferably, the rubber comprises: nitrile rubber, hydrogenated nitrile rubber, natural rubber, styrene-butadiene rubber, and neoprene;
the active agent comprises 1.5-8 parts of zinc oxide and 0.5-4 parts of stearic acid;
the anti-aging agent comprises a 2, 4-trimethyl-1, 2-dihydroquinoline polymer, N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine and N-phenyl-2-naphthylamine;
the carbon black includes N660, N550, N330, and N339;
the plasticizer comprises dioctyl phthalate, pine tar and aromatic hydrocarbon oil;
the accelerator comprises N-cyclohexyl-2-benzothiazole sulfenamide, tetramethylthiuram disulfide, N-dicyclohexyl-2-benzothiazole sulfenamide, hexamethylenetetramine, N-tertiary butyl-2-benzothiazole sulfenamide, tetrabenzyl thiuram disulfide and dibenzothiazyl disulfide;
the vulcanizing agent comprises insoluble sulfur and common sulfur powder;
the aramid comprises chopped aramid and aramid pulp, and the length-diameter ratio of the chopped aramid is 80-500;
the method for treating the aramid fibers by the ionic liquid comprises the following steps:
(1) Adding the ionic liquid into ethanol, and fully dissolving to obtain ionic liquid ethanol solution;
(2) Immersing aramid fiber into the ionic liquid ethanol solution for immersing;
(3) Drying the soaked aramid fibers;
the concentration of the ionic liquid ethanol solution is 0.05-2g/L; the mass ratio of the ionic liquid to the aramid fiber in the ionic liquid ethanol solution is 1:30-1:300; the temperature of the drying is 60-150 ℃;
the ionic liquid comprises cations and anions which contain carbon-carbon double bond structures on side chains; the concentration of the ionic liquid ethanol solution is 0.05-2g/L; the mass ratio of the ionic liquid to the aramid fiber in the ionic liquid ethanol solution is 1:30-1:300; the temperature of the drying is 60-150 ℃;
the cation containing a carbon-carbon double bond structure on the side chain comprises the following structure:
the beneficial effects of the invention are as follows:
according to the invention, the ionic liquid with double bonds on the side chains in the cationic structure is used for treating the aramid fibers, so that the compatibility of the aramid fibers and a rubber matrix and the chemical bonding capability of the aramid fibers and the rubber are improved, and the mechanical property and the wear resistance of the rubber-based composite material are improved. The composite material provided by the invention has the advantages of strong tearing resistance, excellent wear resistance, low wear rate and long service life.
Drawings
FIG. 1 is a scanning electron microscope photograph of an experimental example of the present invention after the abrasion resistance test without adding an aramid group;
FIG. 2 is a scanning electron microscope photograph of an experimental example of the present invention after 15 parts of untreated aramid fiber groups are added for wear resistance test;
FIG. 3 is a scanning electron microscope photograph of an aramid pulp group after 15 parts of 1-carboxymethyl-3-methylimidazole chloride salt is added to the experimental example of the present invention for abrasion resistance test;
FIG. 4 is a scanning electron microscope photograph of an aramid pulp group after 15 parts of 1-allyl-3-vinylimidazole chloride salt treatment is added in an experimental example of the present invention;
Detailed Description
In order to clearly illustrate the technical characteristics of the scheme, the scheme is explained below through a specific embodiment.
Example 1
1. Preparation of aramid pulp treated by ionic liquid ethanol solution
(1) Adding 1-propenyl-3-vinyl imidazole chloride (with the structure shown as the following) ionic liquid into ethanol, and fully dissolving to obtain an ionic liquid ethanol solution with the concentration of 0.222 g/L;
(2) Immersing the aramid pulp into the ionic liquid ethanol solution for immersing, wherein the mass ratio of the ionic liquid to the aramid pulp is 1:100;
(3) Drying the soaked aramid pulp;
2. preparation of high wear-resistant rubber composite material
(1) 100 parts of nitrile rubber, 5 parts of zinc oxide, 1 part of stearic acid, 1.2 parts of 2, 4-trimethyl-1, 2-dihydroquinoline polymer (TMQ), 550 parts of carbon black N, 10 parts of dioctyl phthalate (DOP), and 15 parts of aramid pulp treated by 1-propenyl-3-vinylimidazole chloride ionic liquid are mixed in an internal mixer for 7 minutes at the initial temperature of 90 ℃ to obtain a primary product.
(2) 1 part of N-cyclohexyl-2-benzothiazole sulfenamide and 1.5 parts of insoluble sulfur are added into the primary product, and the mixture is mixed for 10 minutes in an open mill at the initial temperature of 40 ℃ to obtain a semi-finished product after uniform mixing.
(3) And (3) placing the semi-finished product in a die, wherein the vulcanization temperature is 155 ℃, the pressure is 10MPa, and the vulcanization time is 14min, so that the high-wear-resistance rubber-based composite material 1 is obtained.
Example 2
1. Preparation of aramid pulp treated by ionic liquid ethanol solution
(1) Adding 1-propenyl-3-vinyl imidazole chloride (with the structure shown as the following) ionic liquid into ethanol, and fully dissolving to obtain an ionic liquid ethanol solution with the concentration of 0.222 g/L;
(2) Immersing the aramid pulp into the ionic liquid ethanol solution for immersing, wherein the mass ratio of the ionic liquid to the aramid pulp is 1:100;
(3) Drying the soaked aramid pulp;
2. preparation of high wear-resistant rubber composite material
(1) 100 parts of nitrile rubber, 5 parts of zinc oxide, 1 part of stearic acid, 1.2 parts of 2, 4-trimethyl-1, 2-dihydroquinoline polymer (TMQ), 550 parts of carbon black N, 10 parts of dioctyl phthalate (DOP), and 10 parts of aramid pulp treated by 1-propenyl-3-vinylimidazole chloride ionic liquid are mixed in an internal mixer for 7 minutes at the initial temperature of 90 ℃ to obtain a primary product.
(2) 1 part of N-cyclohexyl-2-benzothiazole sulfenamide and 1.5 parts of insoluble sulfur are added into the primary product, and the mixture is mixed for 10 minutes in an open mill at the initial temperature of 40 ℃ to obtain a semi-finished product after uniform mixing.
(3) And (3) placing the semi-finished product in a die, wherein the vulcanization temperature is 155 ℃, the pressure is 10MPa, and the vulcanization time is 14min, so that the high-wear-resistance rubber-based composite material 2 is obtained.
Example 3
1. Preparation of aramid pulp treated by ionic liquid ethanol solution
(1) Adding 1-allyl-3-methylimidazole chloride (with the structure shown as the following) ionic liquid into ethanol, and fully dissolving to obtain an ionic liquid ethanol solution with the concentration of 0.206 g/L;
(2) Immersing the aramid pulp into the ionic liquid ethanol solution for immersing, wherein the mass ratio of the ionic liquid to the aramid pulp is 1:100;
(3) Drying the soaked aramid pulp;
2. preparation of high wear-resistant rubber composite material
(1) 100 parts of nitrile rubber, 5 parts of zinc oxide, 1 part of stearic acid, 1.2 parts of 2, 4-trimethyl-1, 2-dihydroquinoline polymer (TMQ), 550 parts of carbon black N, 10 parts of dioctyl phthalate (DOP), and 15 parts of aramid pulp treated by 1-allyl-3-methylimidazole chloride ionic liquid are mixed in an internal mixer for 7 minutes at the initial temperature of 90 ℃ to obtain a primary product.
(2) 1 part of N-cyclohexyl-2-benzothiazole sulfenamide (CBS) and 1.5 parts of insoluble sulfur are added into the primary product, and the mixture is mixed for 10 minutes in an open mill at the initial temperature of 40 ℃ to obtain a semi-finished product after uniform mixing.
(3) And (3) placing the semi-finished product in a die, wherein the vulcanization temperature is 155 ℃, the pressure is 10MPa, and the vulcanization time is 14min, so that the high-wear-resistance rubber-based composite material 3 is obtained.
Example 4
1. Preparation of aramid pulp treated by ionic liquid ethanol solution
(1) Adding 1-allyl-3-methylimidazole chloride (with the structure shown as the following) ionic liquid into ethanol, and fully dissolving to obtain an ionic liquid ethanol solution with the concentration of 0.206 g/L;
(2) Immersing the aramid pulp into the ionic liquid ethanol solution for immersing, wherein the mass ratio of the ionic liquid to the aramid pulp is 1:100;
(3) Drying the soaked aramid pulp;
2. preparation of high wear-resistant rubber composite material
(1) 100 parts of nitrile rubber, 5 parts of zinc oxide, 1 part of stearic acid, 1.2 parts of 2, 4-trimethyl-1, 2-dihydroquinoline polymer (TMQ), 550 parts of carbon black N, 10 parts of dioctyl phthalate (DOP), and 10 parts of aramid pulp treated by 1-allyl-3-methylimidazole chloride ionic liquid are mixed in an internal mixer for 7 minutes at the initial temperature of 90 ℃ to obtain a primary product.
(2) 1 part of N-cyclohexyl-2-benzothiazole sulfenamide (CBS) and 1.5 parts of insoluble sulfur are added into the primary product, and the mixture is mixed for 10 minutes in an open mill at the initial temperature of 40 ℃ to obtain a semi-finished product after uniform mixing.
(3) And (3) placing the semi-finished product in a die, wherein the vulcanization temperature is 155 ℃, the pressure is 10MPa, and the vulcanization time is 14min, so that the high-wear-resistance rubber-based composite material 4 is obtained.
Example 5
1. Preparation of chopped aramid fibers treated by ionic liquid ethanol solution
(1) Adding 1-propenyl-3-vinyl imidazole chloride (with the structure shown as the following) ionic liquid into ethanol, and fully dissolving to obtain an ionic liquid ethanol solution with the concentration of 0.5 g/L;
(2) Immersing chopped aramid fibers into the ionic liquid ethanol solution for immersing, wherein the length of the chopped aramid fibers is 1mm, the length-diameter ratio is 80:1, and the mass ratio of the ionic liquid to the aramid fibers is 1:50;
(3) Drying the soaked aramid fibers;
2. preparation of high wear-resistant rubber composite material
(1) 100 parts of nitrile rubber, 5 parts of zinc oxide, 1 part of stearic acid, 1.2 parts of 2, 4-trimethyl-1, 2-dihydroquinoline polymer (TMQ), 550 parts of carbon black N, 10 parts of dioctyl phthalate (DOP), and 40 parts of chopped aramid fiber treated by 1-propenyl-3-vinylimidazole chloride ionic liquid are mixed in an internal mixer for 10 minutes at the initial temperature of 60 ℃ to obtain a primary product.
(2) 1 part of N-cyclohexyl-2-benzothiazole sulfenamide (CBS) and 1.5 parts of insoluble sulfur are added into the primary product, and the mixture is mixed for 15 minutes in an open mill at the initial temperature of 40 ℃ to obtain a semi-finished product after uniform mixing.
(3) And (3) placing the semi-finished product in a die, wherein the vulcanization temperature is 165 ℃, the pressure is 10MPa, and the vulcanization time is 10min, so that the high-wear-resistance rubber-based composite material 5 is obtained.
Example 6
1. Preparation of aramid fiber treated by ionic liquid ethanol solution
(1) Adding 1-propenyl-3-vinyl imidazole chloride (with the structure shown as the following) ionic liquid into ethanol, and fully dissolving to obtain an ionic liquid ethanol solution with the concentration of 0.05 g/L;
(2) Immersing chopped aramid fibers into the ionic liquid ethanol solution for immersing, wherein the length of the chopped aramid fibers is 4mm, the length-diameter ratio is 400:1, and the mass ratio of the ionic liquid to the aramid fibers is 1:150;
(3) Drying the soaked aramid fibers;
2. preparation of high wear-resistant rubber composite material
(1) 100 parts of nitrile rubber, 5 parts of zinc oxide, 1 part of stearic acid, 1.2 parts of 2, 4-trimethyl-1, 2-dihydroquinoline polymer (TMQ), 550 parts of carbon black N, 10 parts of dioctyl phthalate (DOP), 15 parts of chopped aramid fiber treated by 1-propenyl-3-vinylimidazole chloride ionic liquid, 1 part of N-cyclohexyl-2-benzothiazole sulfenamide (CBS) and 1.5 parts of insoluble sulfur are mixed in an open mill for 15 minutes at the initial temperature of 40 ℃ to obtain a semi-finished product after uniform mixing.
(2) And (3) placing the semi-finished product in a die, wherein the vulcanization temperature is 150 ℃, the pressure is 10MPa, and the vulcanization time is 20min, so that the high-wear-resistance rubber-based composite material 6 is obtained.
Example 7
1. Preparation of aramid pulp treated by ionic liquid ethanol solution
(1) Adding 1-propenyl-3-vinyl imidazole chloride (with the structure shown as the following) ionic liquid into ethanol, and fully dissolving to obtain an ionic liquid ethanol solution with the concentration of 2g/L;
(2) Immersing the aramid pulp into the ionic liquid ethanol solution for immersing, wherein the mass ratio of the ionic liquid to the aramid pulp is 1:50;
(3) Drying the soaked aramid pulp;
2. preparation of high wear-resistant rubber composite material
(1) 100 parts of natural rubber, 5 parts of zinc oxide, 1 part of stearic acid, 1 part of N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine (6 PPD), 330 parts of carbon black N, 5 parts of pine tar, and 10 parts of aramid pulp treated by 1-allyl-3-methylimidazole chloride ionic liquid are mixed in an internal mixer at an initial temperature of 60 ℃ for 5 minutes to obtain a primary product.
(2) 0.5 part of tetramethylthiuram disulfide (TMTD), 1 part of dibenzothiazyl Disulfide (DM) and 4 parts of common sulfur are added into the primary product, and the mixture is mixed for 6 minutes in an open mill at the initial temperature of 20 ℃ to obtain a semi-finished product after uniform mixing.
(3) And placing the semi-finished product in a die, wherein the vulcanization temperature is 150 ℃, the pressure is 10MPa, and the vulcanization time is 10min, so that the high-wear-resistance rubber-based composite material 7 is obtained.
Example 8
1. Preparation of aramid pulp treated by ionic liquid ethanol solution
(1) Adding 1-propenyl-3-vinyl imidazole chloride (with the structure shown as the following) ionic liquid into ethanol, and fully dissolving to obtain an ionic liquid ethanol solution with the concentration of 0.4 g/L;
(2) Immersing the aramid pulp into the ionic liquid ethanol solution for immersing, wherein the mass ratio of the ionic liquid to the aramid pulp is 1:150;
(3) Drying the soaked aramid pulp;
2. preparation of high wear-resistant rubber composite material
(1) 100 parts of hydrogenated nitrile rubber, 4 parts of zinc oxide, 0.8 part of stearic acid, 1 part of 2, 4-trimethyl-1, 2-dihydroquinoline polymer (TMQ), 550 parts of carbon black N, 10 parts of dioctyl phthalate (DOP), and 15 parts of aramid pulp treated by 1-propenyl-3-vinylimidazole chloride ionic liquid are mixed in an internal mixer for 9 minutes at the initial temperature of 60 ℃ to obtain a primary product.
(2) 1.5 parts of N-tertiary butyl-2-benzothiazole sulfenamide (TBBS) and 1.5 parts of common sulfur are added into the primary product, and the mixture is mixed for 5 minutes in an open mill at the initial temperature of 30 ℃ to obtain a semi-finished product after uniform mixing.
(3) And (3) placing the semi-finished product in a die, wherein the vulcanization temperature is 160 ℃, the pressure is 10MPa, and the vulcanization time is 17min, so that the high-wear-resistance rubber-based composite material 8 is obtained.
Example 9
1. Preparation of aramid pulp treated by ionic liquid ethanol solution
(1) Adding 1-propenyl-3-vinyl imidazole chloride (with the structure shown as the following) ionic liquid into ethanol, and fully dissolving to obtain an ionic liquid ethanol solution with the concentration of 0.1 g/L;
(2) Immersing the aramid pulp into the ionic liquid ethanol solution for immersing, wherein the mass ratio of the ionic liquid to the aramid pulp is 1:120;
(3) Drying the soaked aramid pulp;
2. preparation of high wear-resistant rubber composite material
(1) 100 parts of styrene-butadiene rubber, 2 parts of zinc oxide, 0.5 part of stearic acid, 1 part of 2, 4-trimethyl-1, 2-dihydroquinoline polymer (TMQ), 1.5 parts of N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine (6 PPD), 50 parts of carbon black N, 1 part of aromatic oil and 15 parts of aramid pulp treated by 1-propenyl-3-vinylimidazole chloride ionic liquid are mixed in an internal mixer for 9 minutes at the initial temperature of 60 ℃ to obtain a primary product.
(2) 1.5 parts of N-tertiary butyl-2-benzothiazole sulfenamide (TBBS), 0.5 part of tetrabenzyl thiuram disulfide (TBzTD) and 2 parts of common sulfur are added into the primary product, and the mixture is mixed for 10 minutes in an open mill at the initial temperature of 20 ℃ to obtain a semi-finished product after uniform mixing.
(3) And (3) placing the semi-finished product in a die, wherein the vulcanization temperature is 155 ℃, the pressure is 10MPa, and the vulcanization time is 14min, so that the high-wear-resistance rubber-based composite material 9 is obtained.
Example 10
1. Preparation of aramid pulp treated by ionic liquid ethanol solution
(1) Adding 1-propenyl-3-vinyl imidazole chloride (with the structure shown as the following) ionic liquid into ethanol, and fully dissolving to obtain an ionic liquid ethanol solution with the concentration of 0.3 g/L;
(2) Immersing the aramid pulp into the ionic liquid ethanol solution for immersing, wherein the mass ratio of the ionic liquid to the aramid pulp is 1:80;
(3) Drying the soaked aramid pulp;
2. preparation of high wear-resistant rubber composite material
(1) 100 parts of neoprene rubber, 4.8 parts of magnesium oxide, 2 parts of stearic acid, 1 part of N-phenyl-2-naphthylamine (D), 330 parts of carbon black N, 5 parts of dioctyl phthalate (DOP), and 15 parts of aramid pulp treated by 1-propenyl-3-vinylimidazole chloride ionic liquid are mixed in an internal mixer for 9 minutes at the initial temperature of 60 ℃ to obtain a primary product.
(2) 0.5 part of dibenzothiazyl Disulfide (DM) and 6 parts of zinc oxide and 0.5 part of insoluble sulfur are added into the primary product, and the mixture is mixed for 10 minutes in an open mill at the initial temperature of 20 ℃ to obtain a semi-finished product after uniform mixing.
(3) And placing the semi-finished product in a die, wherein the vulcanization temperature is 155 ℃, the pressure is 10MPa, and the vulcanization time is 20min, so that the high-wear-resistance rubber-based composite material 10 is obtained.
Comparative example 1
(1) 100 parts of nitrile rubber, 5 parts of zinc oxide, 1 part of stearic acid, 1.2 parts of 2, 4-trimethyl-1, 2-dihydroquinoline polymer (TMQ), 550 parts of carbon black N, 10 parts of dioctyl phthalate (DOP) are mixed in an internal mixer at an initial temperature of 90 ℃ for 7 minutes to obtain a primary product.
(2) 1 part of N-cyclohexyl-2-benzothiazole sulfenamide (CBS) and 1.5 parts of insoluble sulfur are added into the primary product, and the mixture is mixed for 10 minutes in an open mill at the initial temperature of 40 ℃ to obtain a semi-finished product after uniform mixing.
(3) And (3) placing the semi-finished product in a die, wherein the vulcanization temperature is 155 ℃, the pressure is 10MPa, and the vulcanization time is 14min, so that the rubber-based composite material 1 is obtained.
Comparative example 2
(1) 100 parts of nitrile rubber, 5 parts of zinc oxide, 1 part of stearic acid, 1.2 parts of 2, 4-trimethyl-1, 2-dihydroquinoline polymer (TMQ), 550 parts of carbon black N, 10 parts of dioctyl phthalate (DOP) and 15 parts of untreated aramid pulp are mixed in an internal mixer at an initial temperature of 90 ℃ for 7 minutes to obtain a primary product.
(2) 1 part of N-cyclohexyl-2-benzothiazole sulfenamide (CBS) and 1.5 parts of insoluble sulfur are added into the primary product, and the mixture is mixed for 10 minutes in an open mill at the initial temperature of 40 ℃ to obtain a semi-finished product after uniform mixing.
(3) And (3) placing the semi-finished product in a die, wherein the vulcanization temperature is 155 ℃, the pressure is 10MPa, and the vulcanization time is 14min, so that the rubber-based composite material 2 is obtained.
Comparative example 3
(1) 100 parts of nitrile rubber, 5 parts of zinc oxide, 1 part of stearic acid, 1.2 parts of 2, 4-trimethyl-1, 2-dihydroquinoline polymer (TMQ), 550 parts of carbon black N, 10 parts of dioctyl phthalate (DOP) and 10 parts of untreated aramid pulp are mixed in an internal mixer at an initial temperature of 90 ℃ for 7 minutes to obtain a primary product.
(2) 1 part of N-cyclohexyl-2-benzothiazole sulfenamide (CBS) and 1.5 parts of insoluble sulfur are added into the primary product, and the mixture is mixed for 10 minutes in an open mill at the initial temperature of 40 ℃ to obtain a semi-finished product after uniform mixing.
(3) And (3) placing the semi-finished product in a die, wherein the vulcanization temperature is 155 ℃, the pressure is 10MPa, and the vulcanization time is 14min, so that the rubber-based composite material 3 is obtained.
Comparative example 4
1. Preparation of aramid pulp treated by ionic liquid ethanol solution
(1) Adding 1-carboxymethyl-3-methylimidazole chloride (with the structure shown in the specification) ionic liquid into ethanol, and fully dissolving to obtain an ionic liquid ethanol solution with the concentration of 0.230 g/L;
(2) Immersing aramid pulp into the ionic liquid ethanol solution for immersing;
(3) Drying the soaked aramid pulp;
2. preparation of rubber composite
(1) 100 parts of nitrile rubber, 5 parts of zinc oxide, 1 part of stearic acid, 1.2 parts of 2, 4-trimethyl-1, 2-dihydroquinoline polymer (TMQ), 550 parts of carbon black N, 10 parts of dioctyl phthalate (DOP), and 15 parts of aramid pulp treated by 1-carboxymethyl-3-methylimidazole chloride ionic liquid are mixed in an internal mixer for 7 minutes at the initial temperature of 90 ℃ to obtain a primary product.
(2) 1 part of N-cyclohexyl-2-benzothiazole sulfenamide (CBS) and 1.5 parts of insoluble sulfur are added into the primary product, and the mixture is mixed for 10 minutes in an open mill at the initial temperature of 40 ℃ to obtain a semi-finished product after uniform mixing.
(3) And (3) placing the semi-finished product in a die, wherein the vulcanization temperature is 155 ℃, the pressure is 10MPa, and the vulcanization time is 14min, so as to obtain the rubber-based composite material 4.
Comparative example 5
1. Preparation of aramid pulp treated by ionic liquid ethanol solution
(1) Adding 1-carboxymethyl-3-methylimidazole chloride (with the structure shown in the specification) ionic liquid into ethanol, and fully dissolving to obtain an ionic liquid ethanol solution with the concentration of 0.230 g/L;
(2) Immersing aramid pulp into the ionic liquid ethanol solution for immersing;
(3) Drying the soaked aramid pulp;
2. preparation of rubber composite
(1) 100 parts of nitrile rubber, 5 parts of zinc oxide, 1 part of stearic acid, 1.2 parts of 2, 4-trimethyl-1, 2-dihydroquinoline polymer (TMQ), 550 parts of carbon black N, 10 parts of dioctyl phthalate (DOP), and 10 parts of aramid pulp treated by 1-carboxymethyl-3-methylimidazole chloride ionic liquid are mixed in an internal mixer for 7 minutes at the initial temperature of 90 ℃ to obtain a primary product.
(2) 1 part of N-cyclohexyl-2-benzothiazole sulfenamide (CBS) and 1.5 parts of insoluble sulfur are added into the primary product, and the mixture is mixed for 10 minutes in an open mill at the initial temperature of 40 ℃ to obtain a semi-finished product after uniform mixing.
(3) And (3) placing the semi-finished product in a die, wherein the vulcanization temperature is 155 ℃, the pressure is 10MPa, and the vulcanization time is 14min, so as to obtain the rubber-based composite material 5.
Experimental example
The abrasion resistance of the high abrasion resistant rubber-based composite materials obtained in examples 1 to 4 and the rubber-based composite materials 1 to 5 obtained in comparative examples 1 to 5 were examined. The test equipment is as follows: the MR-H3B type high-speed ring block abrasion testing machine has the testing conditions that: the pressure was 20N, the rotation speed was 300rpm, the temperature was room temperature, and the time was 90 minutes. The test indexes are as follows: the abrasion mark width after the abrasion of the sample was measured, and the effective abrasion rate of the sample was calculated from the abrasion mark width, and the specific detection results are shown in table 1.
Meanwhile, samples of which the abrasion resistance is tested are photographed by a scanning electron microscope with a magnification of 2000 times, respectively, by adding the aramid fiber pulp group which is not added with the aramid fiber group, adding the untreated aramid fiber pulp group 15 parts, adding the aramid fiber pulp group which is treated by 1-carboxymethyl-3-methylimidazole chloride salt and adding the aramid fiber pulp group which is treated by 15 parts of 1-propenyl-3-vinylimidazole chloride salt, and scanning electron microscope photographs are respectively shown in fig. 1-4.
Table 1 results of abrasion resistance test
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As can be seen from FIGS. 1 to 4 and Table 1, the abrasion resistance of the rubber composite material of the present invention is significantly improved as compared with the conventional abrasion-resistant rubber. This is achieved by improving the adhesion of the aramid fibers to the rubber, and thus the tear resistance of the composite. The tear strength of the above composite is shown in table 2.
TABLE 2 tear resistance test results
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Taking the rubber composite material added with 15 parts of aramid pulp treated by 1-propenyl-3-vinylimidazole chloride salt as an example, the effective wear rate is reduced by about 77%, 35% and 23% under the conditions of 20N pressure, 300rpm rotating speed, room temperature and 90min time compared with the aramid pulp group which is not added with aramid pulp, the untreated aramid pulp group which is added with 15 parts and the aramid pulp group which is added with 15 parts and treated by 1-carboxymethyl-3-methylimidazole chloride salt.
The technical features of the present invention that are not described in the present invention may be implemented by or using the prior art, and are not described in detail herein, but the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, but is also intended to be within the scope of the present invention by those skilled in the art.

Claims (3)

1. The high wear-resistant rubber-based composite material is characterized by comprising the following raw materials in parts by weight: 100 parts of rubber, 2-12 parts of active agent, 0.5-2 parts of anti-aging agent, 20-70 parts of carbon black, 1-20 parts of plasticizer, 0.5-2 parts of vulcanizing agent, 0.5-2 parts of accelerator and 1-50 parts of aramid fiber treated by ionic liquid ethanol solution;
the aramid comprises chopped aramid and aramid pulp, and the length-diameter ratio of the chopped aramid is 80-500;
the method for treating the aramid fibers by the ionic liquid comprises the following steps:
(1) Adding the ionic liquid into ethanol, and fully dissolving to obtain ionic liquid ethanol solution;
(2) Immersing aramid fiber into the ionic liquid ethanol solution for immersing;
(3) Drying the soaked aramid fibers;
the ionic liquid comprises cations and anions which contain carbon-carbon double bond structures on side chains; the concentration of the ionic liquid ethanol solution is 0.05-2g/L; the mass ratio of the ionic liquid to the aramid fiber in the ionic liquid ethanol solution is 1:30-1:300; the temperature of the drying is 60-150 ℃;
the cation having a carbon-carbon double bond structure in the side chain includes the following structure:
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the preparation method of the composite material comprises the following steps:
(1) Mixing rubber, an active agent, an anti-aging agent, carbon black, a plasticizer and aramid fibers treated by ionic liquid ethanol solution in an internal mixer for 5-10min at 60-120 ℃ as an initial temperature to obtain a primary product;
(2) Adding an accelerator and a vulcanizing agent into the primary product, mixing for 5-15min in an open mill at the initial temperature of 20-40 ℃ and uniformly mixing to obtain a semi-finished product;
(3) And (3) placing the semi-finished product into a mould for vulcanization to obtain the high-wear-resistance rubber-based composite material, wherein the vulcanization temperature is 140-170 ℃ and the vulcanization time is 10-20min.
2. The composite of claim 1, wherein the rubber comprises: nitrile rubber, hydrogenated nitrile rubber, natural rubber, styrene-butadiene rubber, and neoprene;
the active agent comprises 1.5-8 parts of zinc oxide and 0.5-4 parts of stearic acid;
the anti-aging agent comprises a 2, 4-trimethyl-1, 2-dihydroquinoline polymer, N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine and N-phenyl-2-naphthylamine;
the carbon black includes N660, N550, N330, and N339;
the plasticizer comprises dioctyl phthalate, pine tar and aromatic hydrocarbon oil;
the accelerator comprises N-cyclohexyl-2-benzothiazole sulfenamide, tetramethylthiuram disulfide, N-dicyclohexyl-2-benzothiazole sulfenamide, hexamethylenetetramine, N-tertiary butyl-2-benzothiazole sulfenamide, tetrabenzyl thiuram disulfide and dibenzothiazyl disulfide;
the vulcanizing agent comprises insoluble sulfur and common sulfur powder.
3. The preparation method of the high wear-resistant rubber-based composite material is characterized by comprising the following steps of:
(1) Mixing rubber, an active agent, an anti-aging agent, carbon black, a plasticizer and aramid fibers treated by ionic liquid ethanol solution in an internal mixer for 5-10min at 60-120 ℃ as an initial temperature to obtain a primary product;
(2) Adding an accelerator and a vulcanizing agent into the primary product, mixing for 5-15min in an open mill at the initial temperature of 20-40 ℃ and uniformly mixing to obtain a semi-finished product;
(3) Vulcanizing the semi-finished product in a mold to obtain a high-wear-resistance rubber-based composite material, wherein the vulcanization temperature is 140-170 ℃ and the vulcanization time is 10-20min;
the rubber comprises: nitrile rubber, hydrogenated nitrile rubber, natural rubber, styrene-butadiene rubber, and neoprene;
the active agent comprises 1.5-8 parts of zinc oxide and 0.5-4 parts of stearic acid;
the anti-aging agent comprises a 2, 4-trimethyl-1, 2-dihydroquinoline polymer, N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine and N-phenyl-2-naphthylamine;
the carbon black includes N660, N550, N330, and N339;
the plasticizer comprises dioctyl phthalate, pine tar and aromatic hydrocarbon oil;
the accelerator comprises N-cyclohexyl-2-benzothiazole sulfenamide, tetramethylthiuram disulfide, N-dicyclohexyl-2-benzothiazole sulfenamide, hexamethylenetetramine, N-tertiary butyl-2-benzothiazole sulfenamide, tetrabenzyl thiuram disulfide and dibenzothiazyl disulfide;
the vulcanizing agent comprises insoluble sulfur and common sulfur powder;
the aramid comprises chopped aramid and aramid pulp, and the length-diameter ratio of the chopped aramid is 80-500;
the method for treating the aramid fibers by the ionic liquid comprises the following steps:
(1) Adding the ionic liquid into ethanol, and fully dissolving to obtain ionic liquid ethanol solution;
(2) Immersing aramid fiber into the ionic liquid ethanol solution for immersing;
(3) Drying the soaked aramid fibers;
the ionic liquid comprises cations and anions which contain carbon-carbon double bond structures on side chains; the concentration of the ionic liquid ethanol solution is 0.05-2g/L; the mass ratio of the ionic liquid to the aramid fiber in the ionic liquid ethanol solution is 1:30-1:300; the temperature of the drying is 60-150 ℃;
the cation containing a carbon-carbon double bond structure on the side chain comprises the following structure:
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， />。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103627055A (en) * 2013-11-08 2014-03-12 青岛科技大学 Method for preparing tire tread rubber by use of modified microcrystalline cellulose
CN104629105A (en) * 2015-01-27 2015-05-20 山东大学 Microcrystalline cellulose reinforced rubber wear-resistant material and preparation method thereof
CN106087411A (en) * 2016-06-06 2016-11-09 深圳市新纶科技股份有限公司 A kind of modifying aramid fiber pulp and preparation method thereof and the brake block manufactured with it
CN109694504A (en) * 2018-12-22 2019-04-30 耿丹风 A kind of preparation method of aramid fiber short fibre enhancing native rubber composite material
CN112321909A (en) * 2020-11-19 2021-02-05 侯光宇 High-strength wear-resistant natural rubber composite material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103627055A (en) * 2013-11-08 2014-03-12 青岛科技大学 Method for preparing tire tread rubber by use of modified microcrystalline cellulose
CN104629105A (en) * 2015-01-27 2015-05-20 山东大学 Microcrystalline cellulose reinforced rubber wear-resistant material and preparation method thereof
CN106087411A (en) * 2016-06-06 2016-11-09 深圳市新纶科技股份有限公司 A kind of modifying aramid fiber pulp and preparation method thereof and the brake block manufactured with it
CN109694504A (en) * 2018-12-22 2019-04-30 耿丹风 A kind of preparation method of aramid fiber short fibre enhancing native rubber composite material
CN112321909A (en) * 2020-11-19 2021-02-05 侯光宇 High-strength wear-resistant natural rubber composite material and preparation method thereof

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