CN108276687B - Nano-microcrystalline NCC (non-volatile-copolymer) reinforced rubber material and preparation method thereof - Google Patents
Nano-microcrystalline NCC (non-volatile-copolymer) reinforced rubber material and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- 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
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- C08K2003/222—Magnesia, i.e. magnesium oxide
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
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- 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
Abstract
The invention provides a nano-microcrystalline NCC reinforced rubber material and a preparation method thereof, wherein the nano-microcrystalline NCC reinforced rubber material is composed of NCC, a chemical auxiliary agent, a modifier and EPDM rubber master batch. The preparation method comprises the following steps: 1) treating NCC with a surfactant; 2) adding EPDM rubber master batch, a modifier and a modified NCC solution into a mixing roll for mixing; 3) adding the anti-aging agent and the mixing material into an internal mixer for internal mixing, adding the rubber vulcanizing agent, kneading and stirring at a high speed, and conveying to an open mill; 4) the mixture is thinly passed through an open mill, so that the EPDM rubber master batch, the modifier and the modified NCC are fully and uniformly mixed, and are input into a screw extruder, and a product is formed through the extruder and an extrusion die; 5) and vulcanizing the extrusion molding product, and obtaining the product after vulcanization. The toughness and the wear resistance of the material are both obviously improved, and the material is low in cost, clean and environment-friendly.
Description
Technical Field
The invention belongs to the field of rubber materials, relates to a rubber material and a preparation method thereof, and particularly relates to a nano microcrystalline NCC reinforced rubber material and a preparation method thereof.
Background
As a high-quality elastic material, rubber has been widely used in various fields. According to different rubber compositions, the performance and the application of the rubber are different, and the rubber gasket is used for common rubber floors and non-slip mats of common household floors and special reinforced rubber gaskets for sealing containers and flanges. Glass fiber, carbon fiber, aramid fiber, synthetic fiber, carbon black and the like are commonly used for reinforcing rubber materials, have the advantages of temperature resistance, pressure resistance, good wear resistance, good solvent resistance and the like, but have a plurality of problems, such as uneven fiber dispersion, infirm bonding between rubber and fiber and the like, so that the fiber reinforcing effect is not ideal. The nano microcrystalline Cellulose (NCC) is used as a natural macromolecular compound derived from a wood material, the strength of a single fiber is as high as 57GPa, the affinity to rubber is good, and the nano microcrystalline Cellulose can be used for replacing the traditional glass fiber, carbon fiber and the like to manufacture a reinforced rubber material.
Patent document CN101555330A, published japanese patent No. 2009.10.14, discloses a fiber reinforced rubber, which is made by kneading a plasticated rubber raw material, a reinforcing agent, fibers and an auxiliary agent to prepare a fiber reinforced rubber product. The patent solves the problem of uneven fiber dispersion in the traditional fiber reinforced rubber preparation process, and the preparation process flow is simple, and the prepared rubber has good elasticity, small compression deformation and excellent physical and mechanical properties. However, the patent uses a large amount of glass fibers as reinforcing fibers, the product has high hardness, and the prepared rubber loses the reinforcing effect of the glass fibers due to the falling of the aged glass fibers in the long-term use process, so that the service life of the reinforced rubber is shortened.
Patent document CN102002173A, published japanese patent No. 2011.04.06, provides a method for preparing a nano microcrystalline cellulose/white carbon black/rubber composite material, wherein rod-shaped nano microcrystalline fibers with the diameter of 20-60 nm and the average length of 300nm are used as reinforcing materials to reinforce rubber. The reinforcing effect of the NCC on the natural rubber in the patent is superior to that of white carbon black, the thermal-oxidative aging resistance of the natural rubber is well improved, the heat generation of the composite material is reduced, and the composite rubber can be prepared by adopting the traditional rubber processing technology. However, the patent uses natural rubber as raw material, and is not suitable for industrial mass production due to limited yield, high price and narrow temperature resistance range.
Patent document CN104761761A, published japanese patent No. 2015.07.08, provides a high-toughness nanofiber-reinforced rubber-based 3D printing material prepared by kneading rubber, a thermoplastic polymer nanofiber reinforcing material, and a solvent. The problem that the traditional powder rubber material is low in strength and poor in toughness and needs to be modified before use is solved, and meanwhile, the prepared rubber-based 3D printing material also has the advantages of being high in bonding strength, simple in production process and the like. But this patent uses acetone, dichloromethane, carbon tetrachloride and other poisonous and harmful solvents to produce, and the production harm is great and not environmental protection, and the increase of a large amount of powder in addition can lead to the rubber material fragility great, and powder reinforcing material often can drop, has reduced the life of rubber.
In addition, patent document CN104629105A, published japanese patent No. 2015.05.20, discloses a microcrystalline cellulose reinforced rubber wear-resistant material and a preparation method thereof, wherein the microcrystalline cellulose reinforced rubber wear-resistant material is prepared from the following main raw materials in parts by weight: 1-35 parts of surface-modified microcrystalline cellulose, wherein the surface of the surface-modified microcrystalline cellulose is coated with a wetting agent or a coupling agent accounting for 1-2% of the weight of the microcrystalline cellulose, and 65-99 parts of a rubber matrix; the process route is that nano microcrystalline cellulose is suspended, loosened and sprayed with an impregnating compound or a coupling agent, heated at 60-120 ℃ until the impregnating compound and the coupling agent are completely spread and impregnated on the surface of the cellulose, and then the microcrystalline cellulose with the modified surface and a rubber matrix are mixed and vulcanized to obtain the nano microcrystalline cellulose. Patent document CN104530504A, published japanese patent No. 2015.04.22, discloses a waste cotton material-based rubber composite material of nano microcrystalline cellulose and a preparation method thereof, the method comprises: stirring natural rubber latex; adding the cotton nano microcrystalline cellulose into the natural rubber latex, and stirring and mixing to obtain a cotton nano microcrystalline cellulose/natural rubber mixture; spreading, demulsifying and coprecipitating, washing and precipitating, and drying to balance weight to obtain a solid cotton nano microcrystalline cellulose/natural rubber mixture; mixing with white carbon black to obtain the required product. However, the properties of the reinforced rubber are still not ideal.
In summary, there is a need for a clean and environment-friendly reinforced rubber material with high toughness, wear resistance, aging resistance, crack resistance and low cost.
Disclosure of Invention
The invention aims to provide a nano microcrystal NCC reinforced rubber material which has the advantages of strong toughness and wear resistance, ageing resistance, crack resistance, low cost, cleanness and environmental protection and a preparation method thereof aiming at the defects in the prior art.
In a first aspect, the nano microcrystalline NCC reinforced rubber material provided by the invention is prepared from the following components in percentage by weight: 1-25% of NCC, 2-15% of chemical auxiliary agent, 5-30% of modifier and the balance of EPDM rubber master batch; the NCC has a diameter of 2-15 nm and a length of 150-400 nm; the chemical auxiliary agent consists of 0.01 to 4 percent of surfactant, 0.5 to 5 percent of age resister and 1.5 to 6 percent of rubber vulcanizing agent, and the weight percentage of the surface activator, the age resister and the rubber vulcanizing agent in all the raw materials is 2 to 15 percent.
As another preferred example, the EPDM rubber masterbatch is powder carbon black reinforced EPDM rubber.
As another preferable example, the powdery carbon black content by weight in the powdery carbon black-reinforced EPDM rubber is 20% to 50%.
As another preferable example, the modifier is one, two or more selected from chloroprene rubber, styrene-butadiene rubber, fluorine rubber and silicone rubber.
As another preferable example, the surfactant is one, two or more selected from KH550, KH560, stearic acid, n-butyl titanate and ethyltrimethoxysilane.
As another preferable example, the anti-aging agent is one, two or more selected from the group consisting of liquid paraffin, modified liquid paraffin, triethyl glyceride and dibutyl phthalate.
As another preferable example, the rubber vulcanizing agent is one, two or more selected from the group consisting of magnesium dimethacrylate, TMTD, epoxy resin, zinc chloride and magnesium oxide.
In a second aspect, the invention provides a method for preparing a nano-microcrystalline NCC reinforced rubber material, which comprises the following steps:
1) treating NCC with a surfactant to obtain a modified NCC solution;
2) adding the EPDM rubber master batch, the modifier and the modified NCC solution into a mixing mill for mixing, wherein the mixing temperature is 120-130 ℃, the mixing time is 3-8 min, and discharging at 110-120 ℃ after mixing to obtain a primary mixed material;
3) adding the anti-aging agent and the primary mixing material into an internal mixer for banburying for 2-10 min, adding a rubber vulcanizing agent, kneading at a high speed, and conveying to an open mill;
4) after the mixture in the step 3) is thinly passed for 2-4 times in an open mill, the EPDM rubber master batch, the modifier and the modified NCC are fully and uniformly mixed, input into a screw extruder, and a product is molded through the extruder and an extrusion die;
5) vulcanizing the molded product obtained in the step 4), wherein the vulcanization temperature is 100-150 ℃, the vulcanization pressure is 1.5-5 MPa, and the vulcanization time is 15-45 min, and then preparing the nano microcrystalline NCC reinforced rubber material after vulcanization.
As another preferable example, the EPDM rubber masterbatch is a powdery carbon black-reinforced EPDM rubber, and the powdery carbon black content in the powdery carbon black-reinforced EPDM rubber is 20% to 50% by weight.
As another preferable example, the anti-aging agent is one, two or more selected from the group consisting of liquid paraffin, modified liquid paraffin, triethyl glyceride and dibutyl phthalate.
Herein, the EPDM rubber masterbatch, i.e., ethylene propylene diene monomer, is a copolymer of ethylene, propylene and a small amount of a non-conjugated diene. KH550 is amino functional silane with chemical name of gamma-aminopropyl triethoxysilane. KH560 is a coupling agent containing epoxy group, chemical name gamma-glycidoxypropyltrimethoxysilane. The TMTD is also called N, N-tetramethyl dithiobisthiocarbonylamine.
The invention has the beneficial effects that:
(1) the raw material composition and the proportion are scientific and reasonable, the toughness of the prepared rubber material is obviously improved, the wear resistance is improved while the toughness is improved, and the aim of enhancing the rubber is fulfilled;
(2) the bonding strength between rubber molecules is high, so that the problem of cracking, failure and damage caused by stress concentration at an interface in the reinforced rubber is avoided;
(3) in the material, the anti-aging agent and the rubber vulcanizing agent have a certain synergistic effect;
(4) the raw materials are few in variety, the cost is low, and the preparation process is simple;
(5) the raw materials do not contain toxic and harmful solvents, and are clean and environment-friendly;
(6) the material of the invention is particularly suitable for producing seals.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary and are not intended to limit the scope of the invention, as various equivalent modifications of the invention will occur to those skilled in the art upon reading the present specification and which fall within the limits of the appended claims.
In the following examples and comparative examples, the NCC is available from israel; the neoprene is available from Langsheng chemical (China) Inc.; the KH560, dibutyl phthalate, TMTD, and magnesium oxide are available from Ningbo Examel New materials, Inc.; the powdered carbon black reinforced EPDM rubber was purchased from Cambot corporation, USA; the fluororubbers are available from DuPont, USA; the ethyl trimethoxysilane was purchased from wacker chemical (china) ltd. The rest of the raw materials are not described in detail and are all commercially available raw materials.
Example 1
The nano microcrystalline NCC reinforced rubber material is prepared from the following components in percentage by weight: 5 percent of NCC, 11.5 percent of chemical auxiliary agent, 5 percent of modifier and the balance of EPDM rubber master batch.
The NCC has a diameter of 2nm and a length of 400 nm.
The chemical auxiliary agent comprises 4% of surfactant, 1.5% of age resister and 6% of rubber vulcanizing agent.
The modifier is chloroprene rubber.
The surfactant is KH 560.
The anti-aging agent is dibutyl phthalate.
The rubber vulcanizing agent is TMTD.
The EPDM rubber master batch is powder carbon black reinforced EPDM rubber, wherein the weight content of the powder carbon black in the powder carbon black reinforced EPDM rubber is 20%.
The preparation method comprises the following steps:
1) treating NCC with a surfactant to obtain a modified NCC solution;
2) adding the EPDM rubber master batch, the modifier and the modified NCC solution into a mixing roll for mixing, wherein the mixing temperature is 120 ℃, the mixing time is 8min, and discharging at 110 ℃ after mixing to obtain a primary mixed material;
3) adding the anti-aging agent and the primary mixed material into an internal mixer for internal mixing for 5min, adding the rubber vulcanizing agent, kneading at a high speed, and conveying to an open mill;
4) after the mixture in the step 3) is thinly passed through an open mill for 4 times, the EPDM rubber master batch, the modifier and the modified NCC are fully and uniformly mixed and input into a screw extruder, and a product is molded through the extruder and an extrusion die;
5) vulcanizing the formed product in the step 4) at the vulcanization temperature of 150 ℃, the vulcanization pressure of 2.5MPa and the vulcanization time of 15min, and preparing the nano microcrystalline NCC reinforced rubber material after vulcanization.
Example 2
The nano microcrystalline NCC reinforced rubber material is prepared from the following components in percentage by weight: 5 percent of NCC, 13.5 percent of chemical auxiliary agent, 5.5 percent of modifier and the balance of EDPM rubber master batch.
The NCC has a diameter of 5nm and a length of 150 nm.
The chemical auxiliary agent comprises 4% of surfactant, 4.5% of age resister and 5% of rubber vulcanizing agent.
The modifier is fluororubber.
The surfactant is ethyl trimethoxy silane.
The anti-aging agent is dibutyl phthalate.
The rubber vulcanizing agent is magnesium oxide.
The EDPM rubber master batch is powder carbon black reinforced EDPM rubber, wherein the weight content of the powder carbon black in the powder carbon black reinforced EPDM rubber is 35%.
The preparation method comprises the following steps:
1) treating NCC with a surfactant to obtain a modified NCC solution;
2) adding the EDPM rubber master batch, the modifier and the modified NCC solution into a mixing roll for mixing at 130 ℃ for 8min, and discharging at 110 ℃ after mixing to obtain a primary mixed material;
3) adding the anti-aging agent and the primary mixed material into an internal mixer for internal mixing for 10min, adding the rubber vulcanizing agent, kneading at a high speed, and conveying to an open mill;
4) after the mixture in the step 3) is thinly passed for 2 times in an open mill, the EPDM rubber master batch, the modifier and the modified NCC are fully and uniformly mixed and input into a screw extruder, and a product is molded through the extruder and an extrusion die;
5) vulcanizing the formed product in the step 4) at the vulcanization temperature of 150 ℃, the vulcanization pressure of 1.5MPa and the vulcanization time of 35min, and preparing the nano microcrystalline NCC reinforced rubber material after vulcanization.
Example 3
The nano microcrystalline NCC reinforced rubber material is prepared from the following components in percentage by weight: 1% of NCC, 2.01% of chemical auxiliary agent, 30% of modifier and the balance of EPDM rubber master batch.
The NCC has a diameter of 15nm and a length of 300 nm.
The chemical auxiliary agent comprises 0.01 percent of surfactant, 0.5 percent of age resister and 1.5 percent of rubber vulcanizing agent.
The modifier is silicon rubber.
The surfactant is KH 550.
The anti-aging agent is liquid paraffin.
The rubber vulcanizing agent is epoxy resin.
The EPDM rubber master batch is powder carbon black reinforced EPDM rubber, wherein the weight content of the powder carbon black in the powder carbon black reinforced EPDM rubber is 50%.
The preparation method comprises the following steps:
1) treating NCC with a surfactant to obtain a modified NCC solution;
2) adding the EPDM rubber master batch, the modifier and the modified NCC solution into a mixing roll for mixing, wherein the mixing temperature is 125 ℃, the mixing time is 3min, and discharging at 120 ℃ after mixing to obtain a primary mixed material;
3) adding the anti-aging agent and the primary mixing material into an internal mixer for internal mixing for 2min, adding the rubber vulcanizing agent, kneading at a high speed, and conveying to an open mill;
4) after the mixture in the step 3) is thinly passed through an open mill for 3 times, the EPDM rubber master batch, the modifier and the modified NCC are fully and uniformly mixed, input into a screw extruder and molded into a product through the extruder and an extrusion die;
5) vulcanizing the formed product in the step 4) at the vulcanization temperature of 100 ℃, the vulcanization pressure of 5MPa and the vulcanization time of 30min, and preparing the nano microcrystalline NCC reinforced rubber material after vulcanization.
Example 4
The nano microcrystalline NCC reinforced rubber material is prepared from the following components in percentage by weight: 25% of NCC, 10% of chemical auxiliary agent, 20% of modifier and the balance of EPDM rubber master batch.
The NCC has a diameter of 2nm and a length of 400 nm.
The chemical auxiliary agent comprises 1% of surfactant, 5% of age resister and 4% of rubber vulcanizing agent.
The modifier is styrene butadiene rubber.
The surfactant is stearic acid.
The anti-aging agent is modified liquid paraffin.
The rubber vulcanizing agent is magnesium dimethacrylate.
The EPDM rubber master batch is powder carbon black reinforced EPDM rubber, wherein the weight content of the powder carbon black in the powder carbon black reinforced EPDM rubber is 20%.
The preparation method comprises the following steps:
1) treating NCC with a surfactant to obtain a modified NCC solution;
2) adding the EPDM rubber master batch, the modifier and the modified NCC solution into a mixing roll for mixing, wherein the mixing temperature is 120 ℃, the mixing time is 5min, and discharging at 115 ℃ after mixing to obtain a primary mixed material;
3) adding the anti-aging agent and the primary mixed material into an internal mixer for internal mixing for 10min, adding the rubber vulcanizing agent, kneading at a high speed, and conveying to an open mill;
4) after the mixture in the step 3) is thinly passed through an open mill for 4 times, the EPDM rubber master batch, the modifier and the modified NCC are fully and uniformly mixed and input into a screw extruder, and a product is molded through the extruder and an extrusion die;
5) vulcanizing the formed product in the step 4) at the vulcanization temperature of 120 ℃, the vulcanization pressure of 5MPa and the vulcanization time of 30min, and preparing the nano microcrystalline NCC reinforced rubber material after vulcanization.
Example 5
The nano microcrystalline NCC reinforced rubber material is prepared from the following components in percentage by weight: 15 percent of NCC, 15 percent of chemical auxiliary agent, 10 percent of modifier and the balance of EPDM rubber master batch.
The NCC has a diameter of 5nm and a length of 150 nm.
The chemical auxiliary agent comprises 4% of surfactant, 5% of age resister and 6% of rubber vulcanizing agent.
The modifier is a mixture of chloroprene rubber and styrene butadiene rubber, and the weight ratio of the chloroprene rubber to the styrene butadiene rubber is 1: 1.
The surfactant is a mixture of KH550 and KH560, and the weight ratio of the KH550 to the KH560 is 1: 1.
The anti-aging agent is triethyl glyceride.
The rubber vulcanizing agent is zinc chloride.
The EPDM rubber master batch is powder carbon black reinforced EPDM rubber, wherein the weight content of the powder carbon black in the powder carbon black reinforced EPDM rubber is 20%.
The preparation method comprises the following steps:
1) treating NCC with a surfactant to obtain a modified NCC solution;
2) adding the EPDM rubber master batch, the modifier and the modified NCC solution into a mixing roll for mixing, wherein the mixing temperature is 120 ℃, the mixing time is 8min, and discharging at 110 ℃ after mixing to obtain a primary mixed material;
3) adding the anti-aging agent and the primary mixed material into an internal mixer for internal mixing for 5min, adding the rubber vulcanizing agent, kneading at a high speed, and conveying to an open mill;
4) after the mixture in the step 3) is thinly passed through an open mill for 4 times, the EPDM rubber master batch, the modifier and the modified NCC are fully and uniformly mixed and input into a screw extruder, and a product is molded through the extruder and an extrusion die;
5) vulcanizing the formed product in the step 4) at the vulcanization temperature of 150 ℃, the vulcanization pressure of 2.5MPa and the vulcanization time of 15min, and preparing the nano microcrystalline NCC reinforced rubber material after vulcanization.
Example 6
The nano microcrystalline NCC reinforced rubber material is prepared from the following components in percentage by weight: 5 percent of NCC, 5 percent of chemical auxiliary agent, 10 percent of modifier and the balance of EPDM rubber master batch.
The NCC has a diameter of 2nm and a length of 400 nm.
The chemical auxiliary agent comprises 1% of surfactant, 2% of age resister and 2% of rubber vulcanizing agent.
The modifier is a mixture of chloroprene rubber, styrene-butadiene rubber and fluororubber, and the weight ratio of the chloroprene rubber to the styrene-butadiene rubber is 1:1: 2.
The surface active agent is tetrabutyl titanate.
The anti-aging agent is a mixture of dibutyl phthalate and liquid paraffin, and the weight ratio of the dibutyl phthalate to the liquid paraffin is 1: 1.
The rubber vulcanizing agent is a mixture of TMTD and magnesium oxide, and the weight ratio of the TMTD to the magnesium oxide is 1: 3.
The EPDM rubber master batch is powder carbon black reinforced EPDM rubber, wherein the weight content of the powder carbon black in the powder carbon black reinforced EPDM rubber is 50%.
The preparation method comprises the following steps:
1) treating NCC with a surfactant to obtain a modified NCC solution;
2) adding the EPDM rubber master batch, the modifier and the modified NCC solution into a mixing roll for mixing, wherein the mixing temperature is 120 ℃, the mixing time is 5min, and discharging at 110 ℃ after mixing to obtain a primary mixed material;
3) adding the anti-aging agent and the primary mixed material into an internal mixer for internal mixing for 5min, adding the rubber vulcanizing agent, kneading at a high speed, and conveying to an open mill;
4) after the mixture in the step 3) is thinly passed through an open mill for 4 times, the EPDM rubber master batch, the modifier and the modified NCC are fully and uniformly mixed and input into a screw extruder, and a product is molded through the extruder and an extrusion die;
5) vulcanizing the molded product in the step 4) at the vulcanization temperature of 150 ℃, the vulcanization pressure of 5MPa and the vulcanization time of 15min, and preparing the nano microcrystalline NCC reinforced rubber material after vulcanization.
Example 7
The nano microcrystalline NCC reinforced rubber material is prepared from the following components in percentage by weight: 5 percent of NCC, 10 percent of chemical auxiliary agent, 15 percent of modifier and the balance of EPDM rubber master batch.
The NCC has a diameter of 2nm and a length of 400 nm.
The chemical auxiliary agent comprises 4% of surfactant, 4% of age resister and 2% of rubber vulcanizing agent.
The modifier is chloroprene rubber.
The surfactant is KH 560.
The anti-aging agent is triethyl glyceride.
The rubber vulcanizing agent is a mixture of magnesium dimethacrylate, zinc chloride and magnesium oxide, and the weight ratio of the magnesium dimethacrylate to the zinc chloride to the magnesium oxide is 1:1: 1.
The EPDM rubber master batch is powder carbon black reinforced EPDM rubber, wherein the weight content of the powder carbon black in the powder carbon black reinforced EPDM rubber is 35%.
The preparation method comprises the following steps:
1) treating NCC with a surfactant to obtain a modified NCC solution;
2) adding the EPDM rubber master batch, the modifier and the modified NCC solution into a mixing roll for mixing, wherein the mixing temperature is 130 ℃, the mixing time is 3min, and discharging at 120 ℃ after mixing to obtain a primary mixed material;
3) adding the anti-aging agent and the primary mixed material into an internal mixer for internal mixing for 10min, adding the rubber vulcanizing agent, kneading at a high speed, and conveying to an open mill;
4) after the mixture in the step 3) is thinly passed through an open mill for 3 times, the EPDM rubber master batch, the modifier and the modified NCC are fully and uniformly mixed, input into a screw extruder and molded into a product through the extruder and an extrusion die;
5) vulcanizing the formed product in the step 4) at the vulcanization temperature of 120 ℃, the vulcanization pressure of 5MPa and the vulcanization time of 30min, and preparing the nano microcrystalline NCC reinforced rubber material after vulcanization.
Example 8
The nano microcrystalline NCC reinforced rubber material is prepared from the following components in percentage by weight: 5 percent of NCC, 10 percent of chemical auxiliary agent, 5.5 percent of modifier and the balance of EDPM rubber master batch.
The NCC has a diameter of 5nm and a length of 150 nm.
The chemical auxiliary agent comprises 1% of surfactant, 3% of age resister and 6% of rubber vulcanizing agent.
The modifier is fluororubber.
The surfactant is stearic acid.
The anti-aging agent is dibutyl phthalate.
The rubber vulcanizing agent is magnesium dimethacrylate.
The EDPM rubber master batch is powder carbon black reinforced EDPM rubber, wherein the weight content of the powder carbon black in the powder carbon black reinforced EPDM rubber is 20%.
The preparation method comprises the following steps:
1) treating NCC with a surfactant to obtain a modified NCC solution;
2) adding the EDPM rubber master batch, the modifier and the modified NCC solution into a mixing roll for mixing at 130 ℃ for 8min, and discharging at 110 ℃ after mixing to obtain a primary mixed material;
3) adding the anti-aging agent and the primary mixed material into an internal mixer for internal mixing for 10min, adding the rubber vulcanizing agent, kneading at a high speed, and conveying to an open mill;
4) after the mixture in the step 3) is thinly passed for 2 times in an open mill, the EPDM rubber master batch, the modifier and the modified NCC are fully and uniformly mixed and input into a screw extruder, and a product is molded through the extruder and an extrusion die;
5) vulcanizing the formed product in the step 4) at the vulcanization temperature of 150 ℃, the vulcanization pressure of 1.5MPa and the vulcanization time of 35min, and preparing the nano microcrystalline NCC reinforced rubber material after vulcanization.
Example 9
The nano microcrystalline NCC reinforced rubber material is prepared from the following components in percentage by weight: 10% of NCC, 8% of chemical auxiliary agent, 5.5% of modifier and the balance of EDPM rubber master batch.
The NCC has a diameter of 5nm and a length of 150 nm.
The chemical auxiliary agent comprises 4% of surfactant, 2% of age resister and 2% of rubber vulcanizing agent.
The modifier is styrene butadiene rubber.
The surfactant is a mixture of KH550 and KH560, and the weight ratio of the KH550 to the KH560 is 1: 1.
The anti-aging agent is dibutyl phthalate.
The rubber vulcanizing agent is magnesium oxide.
The EDPM rubber master batch is powder carbon black reinforced EDPM rubber, wherein the weight content of the powder carbon black in the powder carbon black reinforced EPDM rubber is 50%.
The preparation method comprises the following steps:
1) treating NCC with a surfactant to obtain a modified NCC solution;
2) adding the EDPM rubber master batch, the modifier and the modified NCC solution into a mixing roll for mixing at 130 ℃ for 8min, and discharging at 110 ℃ after mixing to obtain a primary mixed material;
3) adding the anti-aging agent and the primary mixed material into an internal mixer for internal mixing for 10min, adding the rubber vulcanizing agent, kneading at a high speed, and conveying to an open mill;
4) after the mixture in the step 3) is thinly passed for 2 times in an open mill, the EPDM rubber master batch, the modifier and the modified NCC are fully and uniformly mixed and input into a screw extruder, and a product is molded through the extruder and an extrusion die;
5) vulcanizing the formed product in the step 4) at the vulcanization temperature of 150 ℃, the vulcanization pressure of 1.5MPa and the vulcanization time of 35min, and preparing the nano microcrystalline NCC reinforced rubber material after vulcanization.
Example 10
The nano microcrystalline NCC reinforced rubber material is prepared from the following components in percentage by weight: 15% of NCC, 5% of chemical auxiliary agent, 20% of modifier and the balance of EDPM rubber master batch.
The NCC has a diameter of 5nm and a length of 150 nm.
The chemical auxiliary agent comprises 1% of surfactant, 1% of age resister and 3% of rubber vulcanizing agent.
The modifier is a mixture of chloroprene rubber, styrene butadiene rubber and silicon rubber, and the weight ratio of the chloroprene rubber to the styrene butadiene rubber to the silicon rubber is 2:1: 1.
The surfactant is ethyl trimethoxy silane.
The anti-aging agent is dibutyl phthalate.
The rubber vulcanizing agent is a mixture of magnesium dimethacrylate, TMTD and magnesium oxide, and the weight ratio of the magnesium dimethacrylate to the TMTD to the magnesium oxide is 2:1: 2.
The EDPM rubber master batch is powder carbon black reinforced EDPM rubber, wherein the weight content of the powder carbon black in the powder carbon black reinforced EPDM rubber is 20%.
The preparation method comprises the following steps:
1) treating NCC with a surfactant to obtain a modified NCC solution;
2) adding the EDPM rubber master batch, the modifier and the modified NCC solution into a mixing roll for mixing at 130 ℃ for 8min, and discharging at 110 ℃ after mixing to obtain a primary mixed material;
3) adding the anti-aging agent and the primary mixed material into an internal mixer for internal mixing for 10min, adding the rubber vulcanizing agent, kneading at a high speed, and conveying to an open mill;
4) after the mixture in the step 3) is thinly passed through an open mill for 3 times, the EPDM rubber master batch, the modifier and the modified NCC are fully and uniformly mixed, input into a screw extruder and molded into a product through the extruder and an extrusion die;
5) vulcanizing the molded product in the step 4) at the vulcanization temperature of 150 ℃, the vulcanization pressure of 5MPa and the vulcanization time of 15min, and preparing the nano microcrystalline NCC reinforced rubber material after vulcanization.
Comparative example 1
The nano microcrystalline NCC reinforced rubber material is prepared from the following components in percentage by weight: 1% of NCC, 2.01% of chemical auxiliary agent, 30% of modifier and the balance of EPDM rubber master batch.
The NCC has a diameter of 20nm and a length of 500 nm.
The chemical auxiliary agent comprises 0.01 percent of surfactant, 0.5 percent of age resister and 1.5 percent of rubber vulcanizing agent.
The modifier is silicon rubber.
The surfactant is KH 550.
The anti-aging agent is liquid paraffin.
The rubber vulcanizing agent is epoxy resin.
The EPDM rubber master batch is powder carbon black reinforced EPDM rubber, wherein the weight content of the powder carbon black in the powder carbon black reinforced EPDM rubber is 50%.
The preparation method comprises the following steps:
1) treating NCC with a surfactant to obtain a modified NCC solution;
2) adding the EPDM rubber master batch, the modifier and the modified NCC solution into a mixing roll for mixing, wherein the mixing temperature is 125 ℃, the mixing time is 3min, and discharging at 120 ℃ after mixing to obtain a primary mixed material;
3) adding the anti-aging agent and the primary mixing material into an internal mixer for internal mixing for 2min, adding the rubber vulcanizing agent, kneading at a high speed, and conveying to an open mill;
4) after the mixture in the step 3) is thinly passed through an open mill for 3 times, the EPDM rubber master batch, the modifier and the modified NCC are fully and uniformly mixed, input into a screw extruder and molded into a product through the extruder and an extrusion die;
5) vulcanizing the molded product in the step 4) at the vulcanization temperature of 100 ℃, the vulcanization pressure of 5MPa and the vulcanization time of 30min to obtain the nano microcrystalline NCC reinforced rubber material.
Comparative example 2
The nano microcrystalline NCC reinforced rubber material is prepared from the following components in percentage by weight: 5 percent of NCC, 11.5 percent of chemical auxiliary agent, 5 percent of modifier and the balance of natural rubber.
The NCC has a diameter of 2nm and a length of 400 nm.
The chemical auxiliary agent comprises 4% of surfactant, 1.5% of age resister and 6% of rubber vulcanizing agent.
The modifier is chloroprene rubber.
The surfactant is KH 560.
The anti-aging agent is dibutyl phthalate.
The rubber vulcanizing agent is TMTD.
The preparation method comprises the following steps:
1) treating NCC with a surfactant to obtain a modified NCC solution;
2) adding the EPDM rubber master batch, the modifier and the modified NCC solution into a mixing roll for mixing, wherein the mixing temperature is 120 ℃, the mixing time is 8min, and discharging at 110 ℃ after mixing to obtain a primary mixed material;
3) adding the anti-aging agent and the primary mixed material into an internal mixer for internal mixing for 5min, adding the rubber vulcanizing agent, kneading at a high speed, and conveying to an open mill;
4) after the mixture in the step 3) is thinly passed through an open mill for 4 times, the EPDM rubber master batch, the modifier and the modified NCC are fully and uniformly mixed and input into a screw extruder, and a product is molded through the extruder and an extrusion die;
5) vulcanizing the formed product in the step 4) at the vulcanization temperature of 150 ℃, the vulcanization pressure of 2.5MPa and the vulcanization time of 15min, and then preparing the nano microcrystalline NCC reinforced rubber material after vulcanization.
Comparative example 3
The nano microcrystalline NCC reinforced rubber material is prepared from the following components in percentage by weight: 30 percent of NCC, 10 percent of chemical auxiliary agent, 20 percent of modifier and the balance of EPDM rubber master batch.
The NCC has a diameter of 2nm and a length of 400 nm.
The chemical auxiliary agent comprises 1% of surfactant, 5% of age resister and 4% of rubber vulcanizing agent.
The modifier is styrene butadiene rubber.
The surfactant is stearic acid.
The anti-aging agent is modified liquid paraffin.
The rubber vulcanizing agent is magnesium dimethacrylate.
The EPDM rubber master batch is powder carbon black reinforced EPDM rubber, wherein the weight content of the powder carbon black in the powder carbon black reinforced EPDM rubber is 20%.
The preparation method comprises the following steps:
1) treating NCC with a surfactant to obtain a modified NCC solution;
2) adding the EPDM rubber master batch, the modifier and the modified NCC solution into a mixing roll for mixing, wherein the mixing temperature is 120 ℃, the mixing time is 5min, and discharging at 115 ℃ after mixing to obtain a primary mixed material;
3) adding the anti-aging agent and the primary mixed material into an internal mixer for internal mixing for 10min, adding the rubber vulcanizing agent, kneading at a high speed, and conveying to an open mill;
4) after the mixture in the step 3) is thinly passed through an open mill for 4 times, the EPDM rubber master batch, the modifier and the modified NCC are fully and uniformly mixed and input into a screw extruder, and a product is molded through the extruder and an extrusion die;
5) vulcanizing the molded product in the step 4) at the vulcanization temperature of 120 ℃, the vulcanization pressure of 5MPa and the vulcanization time of 30min to obtain the nano microcrystalline NCC reinforced rubber material.
Comparative example 4
The nano microcrystalline NCC reinforced rubber material is prepared from the following components in percentage by weight: 5 percent of NCC, 11.5 percent of chemical auxiliary agent, 5 percent of modifier and the balance of EPDM rubber master batch.
The NCC has a diameter of 2nm and a length of 400 nm.
The chemical auxiliary agent comprises 4% of surfactant, 1.5% of age resister and 6% of rubber vulcanizing agent.
The modifier is chloroprene rubber.
The surfactant is KH 560.
The anti-aging agent is 4-methyl-6-tert-butylphenol.
The rubber vulcanizing agent is TMTD.
The EPDM rubber master batch is powder carbon black reinforced EPDM rubber, wherein the weight content of the powder carbon black in the powder carbon black reinforced EPDM rubber is 20%.
The preparation method comprises the following steps:
1) treating NCC with a surfactant to obtain a modified NCC solution;
2) adding the EPDM rubber master batch, the modifier and the modified NCC solution into a mixing roll for mixing, wherein the mixing temperature is 120 ℃, the mixing time is 8min, and discharging at 110 ℃ after mixing to obtain a primary mixed material;
3) adding the anti-aging agent and the primary mixed material into an internal mixer for internal mixing for 5min, adding the rubber vulcanizing agent, kneading at a high speed, and conveying to an open mill;
4) after the mixture in the step 3) is thinly passed through an open mill for 4 times, the EPDM rubber master batch, the modifier and the modified NCC are fully and uniformly mixed and input into a screw extruder, and a product is molded through the extruder and an extrusion die;
5) vulcanizing the formed product in the step 4) at the vulcanization temperature of 150 ℃, the vulcanization pressure of 2.5MPa and the vulcanization time of 15min, and then preparing the nano microcrystalline NCC reinforced rubber material after vulcanization.
Comparative example 5
The nano microcrystalline NCC reinforced rubber material is prepared from the following components in percentage by weight: 5 percent of NCC, 11.5 percent of chemical auxiliary agent, 5 percent of modifier and the balance of EPDM rubber master batch.
The NCC has a diameter of 2nm and a length of 400 nm.
The chemical auxiliary agent comprises 2% of age resister and 9.5% of rubber vulcanizing agent.
The modifier is chloroprene rubber.
The anti-aging agent is dibutyl phthalate.
The rubber vulcanizing agent is TMTD.
The EPDM rubber master batch is powder carbon black reinforced EPDM rubber, wherein the weight content of the powder carbon black in the powder carbon black reinforced EPDM rubber is 20%.
The preparation method comprises the following steps:
1) adding NCC, EPDM rubber master batch and a modifier into a mixing roll for mixing, wherein the mixing temperature is 120 ℃, the mixing time is 8min, and discharging at 110 ℃ after mixing to obtain a primary mixed material;
2) adding the anti-aging agent and the primary mixed material into an internal mixer for internal mixing for 5min, adding the rubber vulcanizing agent, kneading at a high speed, and conveying to an open mill;
3) after the mixture in the step 2) is thinly passed for 4 times in an open mill, the EPDM rubber master batch, the modifier and the NCC are fully and uniformly mixed and input into a screw extruder, and a product is molded through the extruder and an extrusion die;
4) vulcanizing the molded product in the step 3) at the vulcanization temperature of 150 ℃, the vulcanization pressure of 2.5MPa and the vulcanization time of 15min, and then preparing the nano microcrystalline NCC reinforced rubber material.
Comparative example 6
The nano microcrystalline NCC reinforced rubber material is prepared from the following components in percentage by weight: 5 percent of NCC, 11.5 percent of chemical auxiliary agent, 5 percent of modifier and the balance of EPDM rubber master batch.
The NCC has a diameter of 2nm and a length of 400 nm.
The chemical auxiliary agent comprises 8% of surfactant and 3.5% of anti-aging agent.
The modifier is chloroprene rubber.
The surfactant is KH 560.
The anti-aging agent is dibutyl phthalate.
The EPDM rubber master batch is powder carbon black reinforced EPDM rubber, wherein the weight content of the powder carbon black in the powder carbon black reinforced EPDM rubber is 20%.
The preparation method comprises the following steps:
1) treating NCC with a surfactant to obtain a modified NCC solution;
2) adding the EPDM rubber master batch, the modifier and the modified NCC solution into a mixing roll for mixing, wherein the mixing temperature is 120 ℃, the mixing time is 8min, and discharging at 110 ℃ after mixing to obtain a primary mixed material;
3) adding the anti-aging agent and the primary mixed material into an internal mixer for internal mixing for 5min, and conveying the mixture to an open mill after high-speed kneading;
4) after the mixture in the step 3) is thinly passed through an open mill for 4 times, the EPDM rubber master batch, the modifier and the modified NCC are fully and uniformly mixed and input into a screw extruder, and a product is molded through the extruder and an extrusion die;
5) and (3) treating the formed product in the step 4) at the temperature of 150 ℃ and under the pressure of 2.5MPa for 15min to obtain the nano microcrystalline NCC reinforced rubber material.
Comparative example 7
The nano microcrystalline NCC reinforced rubber material is prepared from the following components in percentage by weight: 1% of NCC, 2.01% of chemical auxiliary agent, 30% of modifier and the balance of EPDM rubber master batch.
The NCC has a diameter of 15nm and a length of 300 nm.
The chemical auxiliary agent comprises 0.01 percent of surfactant, 0.5 percent of age resister and 1.5 percent of rubber vulcanizing agent.
The modifier is silicon rubber.
The surfactant is KH 550.
The anti-aging agent is liquid paraffin.
The rubber vulcanizing agent is epoxy resin.
The EPDM rubber master batch is powder carbon black reinforced EPDM rubber, wherein the weight content of the powder carbon black in the powder carbon black reinforced EPDM rubber is 55%.
The preparation method comprises the following steps:
1) treating NCC with a surfactant to obtain a modified NCC solution;
2) adding the EPDM rubber master batch, the modifier and the modified NCC solution into a mixing roll for mixing, wherein the mixing temperature is 125 ℃, the mixing time is 3min, and discharging at 120 ℃ after mixing to obtain a primary mixed material;
3) adding the anti-aging agent and the primary mixing material into an internal mixer for internal mixing for 2min, adding the rubber vulcanizing agent, kneading at a high speed, and conveying to an open mill;
4) after the mixture in the step 3) is thinly passed through an open mill for 3 times, the EPDM rubber master batch, the modifier and the modified NCC are fully and uniformly mixed, input into a screw extruder and molded into a product through the extruder and an extrusion die;
5) vulcanizing the formed product in the step 4) at the vulcanization temperature of 100 ℃, the vulcanization pressure of 5MPa and the vulcanization time of 30min, and preparing the nano microcrystalline NCC reinforced rubber material after vulcanization.
Example 11 Performance testing
The mechanical properties of the nano-microcrystalline NCC reinforced rubber materials prepared in examples 1 to 10 and comparative examples 1 to 7 were tested according to national standards and the results are shown in table 1. The data show that scientific and reasonable material composition and proportion are selected, so that the nano microcrystal NCC reinforced rubber materials prepared in the examples 1-10 are high in rubber intermolecular bonding strength, and remarkably improved in toughness and wear resistance, and the mechanical properties are remarkably improved compared with those of the materials in the comparative examples 1-7.
TABLE 1 mechanical Properties of NCC reinforced rubber materials prepared in examples 1-10 and comparative examples 1-7
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (3)
1. A nano microcrystalline NCC reinforced rubber material is characterized by being prepared from the following components in percentage by weight: 1-25% of NCC, 2-15% of chemical auxiliary agent, 5-30% of modifier and the balance of EPDM rubber master batch; the NCC has a diameter of 2-15 nm and a length of 150-400 nm; the chemical auxiliary agent consists of 0.01 to 4 percent of surface active agent, 0.5 to 5 percent of age resister and 1.5 to 6 percent of rubber vulcanizing agent; the modifier is selected from one or more than two of chloroprene rubber, styrene-butadiene rubber, fluororubber and silicon rubber; the surfactant is selected from one or more than two of KH550, KH560, stearic acid, n-butyl titanate and ethyltrimethoxysilane; the anti-aging agent is selected from one or more of liquid paraffin, modified liquid paraffin, triethyl glyceride and dibutyl phthalate; the rubber vulcanizing agent is selected from one or more than two of magnesium dimethacrylate, TMTD, epoxy resin, zinc chloride and magnesium oxide; the preparation method of the nano microcrystalline NCC reinforced rubber material comprises the following steps:
1) treating NCC with a surfactant to obtain a modified NCC solution;
2) adding the EPDM rubber master batch, the modifier and the modified NCC solution into a mixing mill for mixing, wherein the mixing temperature is 120-130 ℃, the mixing time is 3-8 min, and discharging at 110-120 ℃ after mixing to obtain a primary mixed material;
3) adding the anti-aging agent and the primary mixing material into an internal mixer for banburying for 2-10 min, adding a rubber vulcanizing agent, kneading at a high speed, and conveying to an open mill;
4) after the mixture in the step 3) is thinly passed for 2-4 times in an open mill, the EPDM rubber master batch, the modifier and the modified NCC are fully and uniformly mixed, input into a screw extruder, and a product is molded through the extruder and an extrusion die;
5) vulcanizing the molded product obtained in the step 4), wherein the vulcanization temperature is 100-150 ℃, the vulcanization pressure is 1.5-5 MPa, and the vulcanization time is 15-45 min, and then preparing the nano microcrystalline NCC reinforced rubber material after vulcanization.
2. The nano-microcrystalline NCC reinforced rubber material of claim 1, wherein the EPDM rubber masterbatch is a powdered carbon black reinforced EPDM rubber.
3. The nanocrystalline NCC reinforced rubber material according to claim 2, characterized in that the powdery carbon black content by weight in the powdery carbon black-reinforced EPDM rubber is 20-50%.
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| CN112266539A (en) * | 2020-10-20 | 2021-01-26 | 上海荣南科技有限公司 | Low-carbon-black type ethylene propylene diene monomer rubber and preparation method thereof |
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| CN113861883A (en) * | 2021-10-05 | 2021-12-31 | 襄阳封神新材料有限公司 | Production process of degradable sealant |
| CN113958085A (en) * | 2021-11-08 | 2022-01-21 | 广东丰能环保科技股份有限公司 | High-elasticity high-aging-resistance three-layer rubber floor tile |
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| CN101974172B (en) * | 2010-10-26 | 2012-10-31 | 华南理工大学 | Preparation method of cellulose nanocrystal/carbon black/natural rubber composite |
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| CN101974172B (en) * | 2010-10-26 | 2012-10-31 | 华南理工大学 | Preparation method of cellulose nanocrystal/carbon black/natural rubber composite |
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