CN111154154A - Graphene natural rubber polymer safety sole composite foaming material and preparation method thereof - Google Patents
Graphene natural rubber polymer safety sole composite foaming material and preparation method thereof Download PDFInfo
- Publication number
- CN111154154A CN111154154A CN202010039917.8A CN202010039917A CN111154154A CN 111154154 A CN111154154 A CN 111154154A CN 202010039917 A CN202010039917 A CN 202010039917A CN 111154154 A CN111154154 A CN 111154154A
- Authority
- CN
- China
- Prior art keywords
- parts
- natural rubber
- graphene
- rubber
- sole composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2423/30—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by oxidation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Landscapes
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
The invention discloses a graphene natural rubber polymer safety sole composite foaming material and a preparation method thereof, wherein the graphene natural rubber polymer safety sole composite foaming material is prepared from the following raw materials in parts by weight: 50-60 parts of natural rubber, 6-10 parts of polyolefin elastomer, 7.5-12.5 parts of ethylene propylene diene monomer, 12-18 parts of nitrile rubber, 6-10 parts of butadiene rubber, 3-5 parts of white carbon black, 2.3-2.8 parts of graphene, 1.3-1.7 parts of zinc oxide, 3-4 parts of heat stabilizer, 3-5 parts of flow promoter and 2-2.6 parts of foaming agent. The graphene natural rubber polymer safe sole composite foaming material disclosed by the invention is excellent in wear resistance; the slip resistance coefficient (dry slip resistance and wet slip resistance) is high, the slip resistance effect is good, and the safety is good; in addition, the tensile strength is high, the mechanical property is good, and the durability is good; the density is low, and the light weight is achieved; is very suitable for being used as a safe sole material and has wide market application prospect.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a graphene natural rubber high polymer safety sole composite foaming material and a preparation method thereof.
Background
Natural Rubber (NR) is a natural polymer compound containing cis-1, 4-polyisoprene as a main component, 91 to 94% of which is rubber hydrocarbon (cis-1, 4-polyisoprene), and the balance of which is non-rubber substances such as protein, fatty acid, ash, saccharides and the like. The material is generally a flaky solid, has the relative density of 0.94, the refractive index of 1.522 and the elastic modulus of 2-4 MPa, is softened at 130-140 ℃, is sticky and soft at 150-160 ℃, and begins to degrade at 200 ℃. Has high elasticity and slight plasticity at normal temperature and is crystallized and hardened at low temperature. Has better alkali resistance but does not resist strong acid. Is insoluble in water, lower ketones and alcohols, and can swell in nonpolar solvents such as chloroform, carbon tetrachloride, etc.
The natural rubber mainly has a macromolecular chain structure, the molecular weight, the distribution and aggregation structure of the molecular weight, the macromolecular chain structural unit of the natural rubber is isoprene, the macromolecular chain is mainly composed of polyisoolefine, the content of the rubber accounts for more than ninety-seven percent, aldehyde groups are arranged on the molecular chain, one aldehyde group is arranged on each macromolecular chain on average, just condensation or reaction with a protein decomposition product is carried out on the aldehyde groups to form branching and crosslinking, so that the viscosity of the rubber in storage is increased, and epoxy groups are arranged on the macromolecular chains of the natural rubber and are more active. The macromolecule end of the natural rubber is generally inferred to be dimethylallyl, the other end of the natural rubber is pyrophosphate, a terminal group, aldehyde group of a molecular chain and polymeric elements are few, the molecular weight range of the natural rubber is wide in the aspects of the molecular weight and the distribution of the molecular weight, the vast majority of the molecular weight is about thirty thousand according to the report from abroad, the strength of the natural raw rubber, the rubber compound and the vulcanized rubber is higher, and the strength of the general natural rubber can reach three megapascals. The main reason for the high mechanical strength of natural rubber is that it is a self-reinforcing rubber series, which, when stretched, orients the macromolecular chains in the direction of stress to form crystals, which act as reinforcement in the amorphous macromolecular fraction, and the same high strength as that without expansion is due to the close agglomeration of the tiny particles in its internal structure.
Natural rubber is a variety with the best coordination between physical and mechanical properties and processing properties in rubber materials, and is widely applied to the fields of daily life, medical treatment and health, transportation, agriculture, scientific experiments, national defense and the like. With the development of society, people put higher demands on the performance of products, such as: the traditional rubber foaming sole has heavy weight, the wear resistance can not meet the requirement, the heat shrinkage resistance is poor, and the rubber foaming sole is often required to be modified.
The graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered to be a revolutionary material in the future. In recent years, many studies have been made on modification of rubber materials with graphene, and excellent effects have been obtained. However, in the application process of graphene, the graphene lamellar structure has strong van der waals force or hydrogen bond lamp interaction, so that the graphene lamellar structure is easy to agglomerate and cannot be uniformly and stably dispersed. In general, organic functional groups such as carboxyl, hydroxyl, amino and the like are modified on the surface of the street graphene through chemical grafting, so that the dispersibility of the graphene in a high molecular polymer is improved. However, the method destroys the crystal structure of the graphene, and greatly influences the performance of the graphene.
In addition, the natural rubber foam materials used at present have the following problems:
1. the wear resistance is poor, the anti-slip (anti-slip) effect is poor, and the safety is still to be improved when the material is used as a safe sole material;
2. after foaming, the tensile strength is greatly reduced, the mechanical property is poor, the durability is poor, and the comprehensive use performance is poor; or low degree of foaming, and does not have good portability.
Disclosure of Invention
Based on the above situation, the invention aims to provide a graphene natural rubber polymer safety sole composite foam material and a preparation method thereof, which can effectively solve the above problems.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the graphene natural rubber polymer safety sole composite foaming material is prepared from the following raw materials in parts by weight:
50-60 parts of natural rubber, 6-10 parts of polyolefin elastomer, 7.5-12.5 parts of ethylene propylene diene monomer, 12-18 parts of nitrile rubber, 6-10 parts of butadiene rubber, 3-5 parts of white carbon black, 2.3-2.8 parts of graphene, 1.3-1.7 parts of zinc oxide, 3-4 parts of heat stabilizer, 3-5 parts of flow promoter and 2-2.6 parts of foaming agent.
Preferably, the graphene natural rubber polymer safety sole composite foaming material is prepared from the following raw materials in parts by weight:
55 parts of natural rubber, 8 parts of polyolefin elastomer, 10 parts of ethylene propylene diene monomer, 15 parts of nitrile rubber, 8 parts of butadiene rubber, 4 parts of white carbon black, 2.5 parts of graphene, 1.5 parts of zinc oxide, 3.5 parts of heat stabilizer, 4 parts of flow promoter and 2.3 parts of foaming agent.
Preferably, the polyolefin elastomer is a mixture formed by mixing an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer and an ethylene-1-octene copolymer, wherein the mass ratio of the ethylene-1-butene copolymer to the ethylene-1-hexene copolymer is 10: (14-18): (6-9).
Preferably, the polyolefin elastomer is a mixture formed by mixing an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer and an ethylene-1-octene copolymer, wherein the mass ratio of the ethylene-1-butene copolymer to the ethylene-1-hexene copolymer is 10: 16: 7.5.
the ethylene-1-butene copolymer, the ethylene-1-hexene copolymer and the ethylene-1-octene copolymer have similar chemical structures, close performances and good compatibility, are distinguished (such as the flexibility of molecular weight is increased in sequence), can form better continuous phases with other matrix materials to be matched with each other and complement each other, and can greatly improve the slip stopping effect (nonpolar ground), elasticity and toughness of the graphene natural rubber polymer safety sole composite foaming material.
Preferably, the flow aid is a mixture formed by mixing maleic anhydride grafted polyethylene and oxidized polyethylene, wherein the mass ratio of the maleic anhydride grafted polyethylene to the oxidized polyethylene is 1: (0.67-0.82).
Preferably, the flow aid is a mixture formed by mixing maleic anhydride grafted polyethylene and oxidized polyethylene, wherein the mass ratio of the maleic anhydride grafted polyethylene to the oxidized polyethylene is 1: 0.74.
preferably, the heat stabilizer is a mixture formed by mixing stearic acid and zinc stearate, wherein the mass ratio of the stearic acid to the zinc stearate is 1: (0.6-0.8).
Preferably, the blowing agent is an AC blowing agent.
The invention also provides a preparation method of the graphene natural rubber polymer safety sole composite foaming material, which comprises the following steps:
A. weighing the following components in parts by weight: natural rubber, polyolefin elastomer, ethylene propylene diene monomer, nitrile rubber, butadiene rubber, white carbon black, graphene, zinc oxide, a heat stabilizer, a flow assistant and a foaming agent;
B. feeding natural rubber into an internal mixer, masticating for 12-14 min at the temperature of 130-135 ℃, and discharging; storing the masticated natural rubber at room temperature for more than 50h for later use;
C. b, feeding the natural rubber subjected to the mastication treatment in the step B, a polyolefin elastomer, ethylene propylene diene monomer, nitrile rubber, butadiene rubber, white carbon black, graphene, zinc oxide, a heat stabilizer and a flow aid into an internal mixer, and internally mixing for 10-14 min at the temperature of 90-95 ℃; then banburying for 9-12 min at the temperature of 102-106 ℃; then adding a foaming agent, banburying for 8-10 min at the temperature of 120-124 ℃, and discharging to obtain a banburying rubber mixture;
D. c, conveying the banburying rubber mixture obtained in the step C into an open mill, thinning for 2-4 times on the open mill, and discharging to obtain an open mill rubber mixture;
E. and finally, feeding the open-mill rubber mixture into a mold for hot-pressing foaming, and cooling and molding to obtain the graphene natural rubber polymer safe sole composite foaming material.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the graphene natural rubber polymer safety sole composite foaming material disclosed by the invention is prepared by selecting raw materials, optimizing the content of each raw material, and selecting natural rubber, a polyolefin elastomer, ethylene propylene diene monomer, nitrile rubber, butadiene rubber, white carbon black, graphene, zinc oxide, a heat stabilizer, a flow assistant and a foaming agent in a proper ratio, so that the advantages of the graphene natural rubber polymer safety sole composite foaming material are fully exerted, the graphene natural rubber polymer safety sole composite foaming material is complementary and promoted, the quality stability of a product is improved, and the prepared graphene natural rubber polymer safety sole composite foaming material is excellent in wear resistance; the slip resistance coefficient (dry slip resistance and wet slip resistance) is high, the slip resistance effect is good, and the safety is good; in addition, the tensile strength is high, the mechanical property is good, and the durability is good; the density is low, and the light weight is achieved; is very suitable for being used as a safe sole material and has wide market application prospect.
In the raw materials of the graphene natural rubber polymer safety sole composite foaming material, natural rubber, a polyolefin elastomer, ethylene propylene diene monomer, nitrile rubber and butadiene rubber are used as composite base materials, and the natural rubber is used as a main base material and is nonpolar; the addition of the polyolefin elastomer is mainly used for improving the non-slip effect (non-polar ground), the elasticity and the toughness, and the non-polarity; the ethylene propylene diene monomer rubber has moderate polarity, is used for improving the mechanical property, elasticity and toughness after being added, and can also improve the anti-slip effect on the ground (base surface) with weaker polarity; the nitrile rubber has stronger polarity, improves the anti-slip effect on polar ground (base surface) and improves the wear resistance; the butadiene rubber is non-polar and is mainly used for improving the mechanical property, elasticity and toughness after being added; the graphene natural rubber polymer safety sole composite foam material is matched with each other, so that a good synergistic effect is achieved, and the excellent wear resistance of the graphene natural rubber polymer safety sole composite foam material is well ensured; the slip resistance coefficient (dry slip resistance and wet slip resistance) is high, the slip resistance effect is good, and the safety is good; in addition, the tensile strength is high, the mechanical property is good, and the durability is good; and has low density and ultra-light weight.
The graphene natural rubber polymer safety sole composite foaming material is uniformly dispersed in a raw material system, has a regular shape and a compact structure, and stably exists in a rubber base material in a laminated, stable and uniformly distributed special structural mode, is uniformly dispersed in the raw material system, has good compatibility with other components, is matched with the other components, plays a good synergistic effect, can be uniformly dispersed in a matrix, greatly improves the tensile strength of the graphene natural rubber polymer safety sole composite foaming material, and ensures good mechanical properties; meanwhile, the wear resistance of the graphene natural rubber polymer safety sole composite foaming material is improved.
The white carbon black with a proper proportion is added into the raw materials of the graphene natural rubber polymer safety sole composite foaming material, so that the graphene natural rubber polymer safety sole composite foaming material is uniformly dispersed in a raw material system, has good compatibility with other components, is matched with each other, plays a good synergistic effect, can be uniformly dispersed in a matrix, greatly improves the tensile strength of the graphene natural rubber polymer safety sole composite foaming material, and ensures good mechanical properties; meanwhile, the wear resistance of the graphene natural rubber polymer safety sole composite foaming material is improved.
The graphene natural rubber polymer safety sole composite foaming material disclosed by the invention is prepared by adding a proper amount of flow additive into raw materials, preferably a mixture formed by mixing maleic anhydride grafted polyethylene and oxidized polyethylene, and mainly plays a good lubricating role, increases the processing fluidity, and improves the processing performance and the apparent performance of a product; the compatibility of each component in the raw material system is increased, and the mechanical properties of the material and the like are ensured.
The preparation method has simple process and simple and convenient operation, and saves manpower and equipment cost.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with specific examples, which should not be construed as limiting the present patent.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are conventionally obtained commercially or prepared by conventional methods.
Example 1:
the graphene natural rubber polymer safety sole composite foaming material is prepared from the following raw materials in parts by weight:
50-60 parts of natural rubber, 6-10 parts of polyolefin elastomer, 7.5-12.5 parts of ethylene propylene diene monomer, 12-18 parts of nitrile rubber, 6-10 parts of butadiene rubber, 3-5 parts of white carbon black, 2.3-2.8 parts of graphene, 1.3-1.7 parts of zinc oxide, 3-4 parts of heat stabilizer, 3-5 parts of flow promoter and 2-2.6 parts of foaming agent.
In this embodiment, the graphene natural rubber polymer safety sole composite foaming material is prepared from the following raw materials in parts by weight:
55 parts of natural rubber, 8 parts of polyolefin elastomer, 10 parts of ethylene propylene diene monomer, 15 parts of nitrile rubber, 8 parts of butadiene rubber, 4 parts of white carbon black, 2.5 parts of graphene, 1.5 parts of zinc oxide, 3.5 parts of heat stabilizer, 4 parts of flow promoter and 2.3 parts of foaming agent.
In this embodiment, the polyolefin elastomer is a mixture of an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, and an ethylene-1-octene copolymer, wherein the mass ratio of the three is 10: (14-18): (6-9).
In this embodiment, the polyolefin elastomer is a mixture of an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, and an ethylene-1-octene copolymer, wherein the mass ratio of the three is 10: 16: 7.5.
in this embodiment, the flow aid is a mixture of maleic anhydride grafted polyethylene and oxidized polyethylene, wherein the mass ratio of the maleic anhydride grafted polyethylene to the oxidized polyethylene is 1: (0.67-0.82).
In this embodiment, the flow aid is a mixture of maleic anhydride grafted polyethylene and oxidized polyethylene, wherein the mass ratio of the maleic anhydride grafted polyethylene to the oxidized polyethylene is 1: 0.74.
in this embodiment, the heat stabilizer is a mixture of stearic acid and zinc stearate, wherein the mass ratio of stearic acid to zinc stearate is 1: (0.6-0.8).
In this example, the blowing agent was an AC blowing agent.
The embodiment also provides a preparation method of the graphene natural rubber polymer safety sole composite foam material, which comprises the following steps:
A. weighing the following components in parts by weight: natural rubber, polyolefin elastomer, ethylene propylene diene monomer, nitrile rubber, butadiene rubber, white carbon black, graphene, zinc oxide, a heat stabilizer, a flow assistant and a foaming agent;
B. feeding natural rubber into an internal mixer, masticating for 12-14 min at the temperature of 130-135 ℃, and discharging; storing the masticated natural rubber at room temperature for more than 50h for later use;
C. b, feeding the natural rubber subjected to the mastication treatment in the step B, a polyolefin elastomer, ethylene propylene diene monomer, nitrile rubber, butadiene rubber, white carbon black, graphene, zinc oxide, a heat stabilizer and a flow aid into an internal mixer, and internally mixing for 10-14 min at the temperature of 90-95 ℃; then banburying for 9-12 min at the temperature of 102-106 ℃; then adding a foaming agent, banburying for 8-10 min at the temperature of 120-124 ℃, and discharging to obtain a banburying rubber mixture;
D. c, conveying the banburying rubber mixture obtained in the step C into an open mill, thinning for 2-4 times on the open mill, and discharging to obtain an open mill rubber mixture;
E. and finally, feeding the open-mill rubber mixture into a mold for hot-pressing foaming, and cooling and molding to obtain the graphene natural rubber polymer safe sole composite foaming material.
Example 2:
the graphene natural rubber polymer safety sole composite foaming material is prepared from the following raw materials in parts by weight:
50 parts of natural rubber, 6 parts of polyolefin elastomer, 7.5 parts of ethylene propylene diene monomer, 12 parts of nitrile rubber, 6 parts of butadiene rubber, 3 parts of white carbon black, 2.3 parts of graphene, 1.3 parts of zinc oxide, 3 parts of heat stabilizer, 3 parts of flow promoter and 2 parts of foaming agent.
In this embodiment, the polyolefin elastomer is a mixture of an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, and an ethylene-1-octene copolymer, wherein the mass ratio of the three is 10: 14: 6.
in this embodiment, the flow aid is a mixture of maleic anhydride grafted polyethylene and oxidized polyethylene, wherein the mass ratio of the maleic anhydride grafted polyethylene to the oxidized polyethylene is 1: 0.67.
in this embodiment, the heat stabilizer is a mixture of stearic acid and zinc stearate, wherein the mass ratio of stearic acid to zinc stearate is 1: 0.6.
in this example, the blowing agent was an AC blowing agent.
In this embodiment, the preparation method of the graphene natural rubber polymer safety sole composite foam material includes the following steps:
A. weighing the following components in parts by weight: natural rubber, polyolefin elastomer, ethylene propylene diene monomer, nitrile rubber, butadiene rubber, white carbon black, graphene, zinc oxide, a heat stabilizer, a flow assistant and a foaming agent;
B. feeding natural rubber into an internal mixer, masticating for 14min at the temperature of 130 ℃, and discharging; storing the masticated natural rubber at room temperature for more than 50h for later use;
C. b, feeding the natural rubber subjected to the mastication treatment in the step B, a polyolefin elastomer, ethylene propylene diene monomer, nitrile rubber, butadiene rubber, white carbon black, graphene, zinc oxide, a heat stabilizer and a flow aid into an internal mixer, and internally mixing for 14min at the temperature of 90 ℃; then banburying for 12min at the temperature of 102 ℃; then adding a foaming agent, banburying for 10min at the temperature of 120 ℃, and discharging to obtain a banburying rubber mixture;
D. c, conveying the banburying rubber mixture obtained in the step C into an open mill, thinning for 2 times on the open mill, and discharging to obtain an open mill rubber mixture;
E. and finally, feeding the open-mill rubber mixture into a mold for hot-pressing foaming, and cooling and molding to obtain the graphene natural rubber polymer safe sole composite foaming material.
Example 3:
the graphene natural rubber polymer safety sole composite foaming material is prepared from the following raw materials in parts by weight:
60 parts of natural rubber, 10 parts of polyolefin elastomer, 12.5 parts of ethylene propylene diene monomer, 18 parts of nitrile rubber, 10 parts of butadiene rubber, 5 parts of white carbon black, 2.8 parts of graphene, 1.7 parts of zinc oxide, 4 parts of heat stabilizer, 5 parts of flow promoter and 2.6 parts of foaming agent.
In this embodiment, the polyolefin elastomer is a mixture of an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, and an ethylene-1-octene copolymer, wherein the mass ratio of the three is 10: 18: 9.
in this embodiment, the flow aid is a mixture of maleic anhydride grafted polyethylene and oxidized polyethylene, wherein the mass ratio of the maleic anhydride grafted polyethylene to the oxidized polyethylene is 1: 0.82.
in this embodiment, the heat stabilizer is a mixture of stearic acid and zinc stearate, wherein the mass ratio of stearic acid to zinc stearate is 1: 0.8.
in this example, the blowing agent was an AC blowing agent.
In this embodiment, the preparation method of the graphene natural rubber polymer safety sole composite foam material includes the following steps:
A. weighing the following components in parts by weight: natural rubber, polyolefin elastomer, ethylene propylene diene monomer, nitrile rubber, butadiene rubber, white carbon black, graphene, zinc oxide, a heat stabilizer, a flow assistant and a foaming agent;
B. feeding natural rubber into an internal mixer, masticating for 12min at the temperature of 135 ℃, and discharging; storing the masticated natural rubber at room temperature for more than 50h for later use;
C. b, feeding the natural rubber subjected to the mastication treatment in the step B, a polyolefin elastomer, ethylene propylene diene monomer, nitrile rubber, butadiene rubber, white carbon black, graphene, zinc oxide, a heat stabilizer and a flow aid into an internal mixer, and internally mixing for 10min at the temperature of 95 ℃; then banburying for 9min at the temperature of 106 ℃; then adding a foaming agent, banburying for 8min at the temperature of 124 ℃, and discharging to obtain a banburying rubber mixture;
D. c, conveying the banburying rubber mixture obtained in the step C into an open mill, thinning for 4 times on the open mill, and discharging to obtain an open mill rubber mixture;
E. and finally, feeding the open-mill rubber mixture into a mold for hot-pressing foaming, and cooling and molding to obtain the graphene natural rubber polymer safe sole composite foaming material.
Example 4:
the graphene natural rubber polymer safety sole composite foaming material is prepared from the following raw materials in parts by weight:
55 parts of natural rubber, 8 parts of polyolefin elastomer, 10 parts of ethylene propylene diene monomer, 15 parts of nitrile rubber, 8 parts of butadiene rubber, 4 parts of white carbon black, 2.5 parts of graphene, 1.5 parts of zinc oxide, 3.5 parts of heat stabilizer, 4 parts of flow promoter and 2.3 parts of foaming agent.
In this embodiment, the polyolefin elastomer is a mixture of an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, and an ethylene-1-octene copolymer, wherein the mass ratio of the three is 10: 16: 7.5.
in this embodiment, the flow aid is a mixture of maleic anhydride grafted polyethylene and oxidized polyethylene, wherein the mass ratio of the maleic anhydride grafted polyethylene to the oxidized polyethylene is 1: 0.74.
in this embodiment, the heat stabilizer is a mixture of stearic acid and zinc stearate, wherein the mass ratio of stearic acid to zinc stearate is 1: 0.7.
in this example, the blowing agent was an AC blowing agent.
In this embodiment, the preparation method of the graphene natural rubber polymer safety sole composite foam material includes the following steps:
A. weighing the following components in parts by weight: natural rubber, polyolefin elastomer, ethylene propylene diene monomer, nitrile rubber, butadiene rubber, white carbon black, graphene, zinc oxide, a heat stabilizer, a flow assistant and a foaming agent;
B. feeding natural rubber into an internal mixer, masticating for 13min at the temperature of 132 ℃, and discharging; storing the masticated natural rubber at room temperature for more than 50h for later use;
C. b, feeding the natural rubber subjected to the mastication treatment in the step B, a polyolefin elastomer, ethylene propylene diene monomer, nitrile rubber, butadiene rubber, white carbon black, graphene, zinc oxide, a heat stabilizer and a flow aid into an internal mixer, and internally mixing for 12min at the temperature of 92 ℃; then banburying for 10min at the temperature of 104 ℃; then adding a foaming agent, banburying for 9min at the temperature of 122 ℃, and discharging to obtain a banburying rubber mixture;
D. c, conveying the banburying rubber mixture obtained in the step C into an open mill, thinning for 3 times on the open mill, and discharging to obtain an open mill rubber mixture;
E. and finally, feeding the open-mill rubber mixture into a mold for hot-pressing foaming, and cooling and molding to obtain the graphene natural rubber polymer safe sole composite foaming material.
The graphene natural rubber polymer safety sole composite foam material obtained in the embodiments 2 to 4 of the present invention and the common natural rubber foam material are subjected to performance tests, and the test results are shown in table 1:
TABLE 1
As can be seen from the above table, compared with the common natural rubber foam material, the graphene natural rubber polymer safety sole composite foam material of the present invention has the following advantages: the wear resistance is excellent; the slip resistance coefficient (dry slip resistance and wet slip resistance) is high, the slip resistance effect is good, and the safety is good; in addition, the tensile strength is high, the mechanical property is good, and the durability is good; the density is low, and the light weight is achieved; is very suitable for being used as a safe sole material.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (9)
1. The graphene natural rubber polymer safety sole composite foaming material is characterized by being prepared from the following raw materials in parts by weight:
50-60 parts of natural rubber, 6-10 parts of polyolefin elastomer, 7.5-12.5 parts of ethylene propylene diene monomer, 12-18 parts of nitrile rubber, 6-10 parts of butadiene rubber, 3-5 parts of white carbon black, 2.3-2.8 parts of graphene, 1.3-1.7 parts of zinc oxide, 3-4 parts of heat stabilizer, 3-5 parts of flow promoter and 2-2.6 parts of foaming agent.
2. The graphene natural rubber polymer safety sole composite foam material according to claim 1, which is prepared from the following raw materials in parts by weight:
55 parts of natural rubber, 8 parts of polyolefin elastomer, 10 parts of ethylene propylene diene monomer, 15 parts of nitrile rubber, 8 parts of butadiene rubber, 4 parts of white carbon black, 2.5 parts of graphene, 1.5 parts of zinc oxide, 3.5 parts of heat stabilizer, 4 parts of flow promoter and 2.3 parts of foaming agent.
3. The graphene natural rubber polymer safety sole composite foam material according to claim 1, wherein the polyolefin elastomer is a mixture of an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer and an ethylene-1-octene copolymer, and the mass ratio of the three is 10: (14-18): (6-9).
4. The graphene natural rubber polymer safety sole composite foam material according to claim 2, wherein the polyolefin elastomer is a mixture of an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer and an ethylene-1-octene copolymer, and the mass ratio of the three is 10: 16: 7.5.
5. the graphene natural rubber polymer safety sole composite foam material according to claim 1, wherein the flow aid is a mixture of maleic anhydride grafted polyethylene and oxidized polyethylene, and the mass ratio of the maleic anhydride grafted polyethylene to the oxidized polyethylene is 1: (0.67-0.82).
6. The graphene natural rubber polymer safety sole composite foam material according to claim 2, wherein the flow aid is a mixture of maleic anhydride grafted polyethylene and oxidized polyethylene, and the mass ratio of the maleic anhydride grafted polyethylene to the oxidized polyethylene is 1: 0.74.
7. the graphene natural rubber polymer safety sole composite foam material as claimed in claim 1, wherein the heat stabilizer is a mixture of stearic acid and zinc stearate, and the mass ratio of the stearic acid to the zinc stearate is 1: (0.6-0.8).
8. The graphene natural rubber polymer safety sole composite foam material according to claim 1, wherein the foaming agent is an AC foaming agent.
9. The preparation method of the graphene natural rubber polymer safety sole composite foam material as claimed in any one of claims 1 to 8, which is characterized by comprising the following steps:
A. weighing the following components in parts by weight: natural rubber, polyolefin elastomer, ethylene propylene diene monomer, nitrile rubber, butadiene rubber, white carbon black, graphene, zinc oxide, a heat stabilizer, a flow assistant and a foaming agent;
B. feeding natural rubber into an internal mixer, masticating for 12-14 min at the temperature of 130-135 ℃, and discharging; storing the masticated natural rubber at room temperature for more than 50h for later use;
C. b, feeding the natural rubber subjected to the mastication treatment in the step B, a polyolefin elastomer, ethylene propylene diene monomer, nitrile rubber, butadiene rubber, white carbon black, graphene, zinc oxide, a heat stabilizer and a flow aid into an internal mixer, and internally mixing for 10-14 min at the temperature of 90-95 ℃; then banburying for 9-12 min at the temperature of 102-106 ℃; then adding a foaming agent, banburying for 8-10 min at the temperature of 120-124 ℃, and discharging to obtain a banburying rubber mixture;
D. c, conveying the banburying rubber mixture obtained in the step C into an open mill, thinning for 2-4 times on the open mill, and discharging to obtain an open mill rubber mixture;
and finally, feeding the open-mill rubber mixture into a mold for hot-pressing foaming, and cooling and molding to obtain the graphene natural rubber polymer safe sole composite foaming material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010039917.8A CN111154154A (en) | 2020-01-15 | 2020-01-15 | Graphene natural rubber polymer safety sole composite foaming material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010039917.8A CN111154154A (en) | 2020-01-15 | 2020-01-15 | Graphene natural rubber polymer safety sole composite foaming material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111154154A true CN111154154A (en) | 2020-05-15 |
Family
ID=70562881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010039917.8A Pending CN111154154A (en) | 2020-01-15 | 2020-01-15 | Graphene natural rubber polymer safety sole composite foaming material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111154154A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876779A (en) * | 2021-01-21 | 2021-06-01 | 福建五持恒科技发展有限公司 | Graphene composite material with high slip resistance and suitable for walking stick |
| CN113243609A (en) * | 2021-05-20 | 2021-08-13 | 温州市巨伦鞋业有限公司 | Anti-skid labor protection shoe and preparation method thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106046460A (en) * | 2016-07-14 | 2016-10-26 | 吴明才 | High-elasticity wear-resistant rubber shoe sole material and preparation method thereof |
| CN109181025A (en) * | 2018-09-01 | 2019-01-11 | 成都市水泷头化工科技有限公司 | A kind of anti-skidding natural rubber material and preparation method for athletic shoe sole |
| CN109233005A (en) * | 2018-08-18 | 2019-01-18 | 鹤山市金俊达新材料有限公司 | A kind of Light rubber and preparation method thereof for sole |
| CN109627512A (en) * | 2019-01-08 | 2019-04-16 | 福建五持恒科技发展有限公司 | Sole ultralight graphene rubber pange micelle and preparation method thereof |
| CN110183770A (en) * | 2019-06-05 | 2019-08-30 | 福建五持恒科技发展有限公司 | A kind of rubber-plastic foamed sole micelle of graphene and preparation method thereof |
| CN110511451A (en) * | 2019-10-12 | 2019-11-29 | 福建五持恒科技发展有限公司 | A kind of graphene arctic rubber polymeric composition and preparation method thereof |
| CN110511452A (en) * | 2019-10-14 | 2019-11-29 | 福建五持恒科技发展有限公司 | Graphene natural rubber macromolecule control bacterium mixed foaming material and preparation method thereof |
| CN110607000A (en) * | 2019-10-14 | 2019-12-24 | 福建五持恒科技发展有限公司 | Graphene natural rubber oil-resistant mixed foam material and preparation method thereof |
| CN110628123A (en) * | 2019-10-12 | 2019-12-31 | 石狮市创意纸塑制品有限公司 | High-strength tear-resistant drop and manufacturing process thereof |
| CN110628095A (en) * | 2019-10-12 | 2019-12-31 | 福建五持恒科技发展有限公司 | Graphene high-elasticity rubber elastomer high polymer material and preparation method thereof |
| CN110684245A (en) * | 2019-10-14 | 2020-01-14 | 福建五持恒科技发展有限公司 | Graphene natural rubber polymer static-control mixed foam material and preparation method thereof |
| CN110684244A (en) * | 2019-10-12 | 2020-01-14 | 福建五持恒科技发展有限公司 | Graphene natural rubber foamed polymer composite material and preparation method thereof |
-
2020
- 2020-01-15 CN CN202010039917.8A patent/CN111154154A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106046460A (en) * | 2016-07-14 | 2016-10-26 | 吴明才 | High-elasticity wear-resistant rubber shoe sole material and preparation method thereof |
| CN109233005A (en) * | 2018-08-18 | 2019-01-18 | 鹤山市金俊达新材料有限公司 | A kind of Light rubber and preparation method thereof for sole |
| CN109181025A (en) * | 2018-09-01 | 2019-01-11 | 成都市水泷头化工科技有限公司 | A kind of anti-skidding natural rubber material and preparation method for athletic shoe sole |
| CN109627512A (en) * | 2019-01-08 | 2019-04-16 | 福建五持恒科技发展有限公司 | Sole ultralight graphene rubber pange micelle and preparation method thereof |
| CN110183770A (en) * | 2019-06-05 | 2019-08-30 | 福建五持恒科技发展有限公司 | A kind of rubber-plastic foamed sole micelle of graphene and preparation method thereof |
| CN110511451A (en) * | 2019-10-12 | 2019-11-29 | 福建五持恒科技发展有限公司 | A kind of graphene arctic rubber polymeric composition and preparation method thereof |
| CN110628123A (en) * | 2019-10-12 | 2019-12-31 | 石狮市创意纸塑制品有限公司 | High-strength tear-resistant drop and manufacturing process thereof |
| CN110628095A (en) * | 2019-10-12 | 2019-12-31 | 福建五持恒科技发展有限公司 | Graphene high-elasticity rubber elastomer high polymer material and preparation method thereof |
| CN110684244A (en) * | 2019-10-12 | 2020-01-14 | 福建五持恒科技发展有限公司 | Graphene natural rubber foamed polymer composite material and preparation method thereof |
| CN110511452A (en) * | 2019-10-14 | 2019-11-29 | 福建五持恒科技发展有限公司 | Graphene natural rubber macromolecule control bacterium mixed foaming material and preparation method thereof |
| CN110607000A (en) * | 2019-10-14 | 2019-12-24 | 福建五持恒科技发展有限公司 | Graphene natural rubber oil-resistant mixed foam material and preparation method thereof |
| CN110684245A (en) * | 2019-10-14 | 2020-01-14 | 福建五持恒科技发展有限公司 | Graphene natural rubber polymer static-control mixed foam material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876779A (en) * | 2021-01-21 | 2021-06-01 | 福建五持恒科技发展有限公司 | Graphene composite material with high slip resistance and suitable for walking stick |
| CN113243609A (en) * | 2021-05-20 | 2021-08-13 | 温州市巨伦鞋业有限公司 | Anti-skid labor protection shoe and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110698733B (en) | Graphene natural rubber polymer ice top-slip mixed foam material and preparation method thereof | |
| CN110684244A (en) | Graphene natural rubber foamed polymer composite material and preparation method thereof | |
| CN110628095A (en) | Graphene high-elasticity rubber elastomer high polymer material and preparation method thereof | |
| US4348502A (en) | Thermoplastic compositions of nylon and ethylene-vinyl acetate rubber | |
| CN111154154A (en) | Graphene natural rubber polymer safety sole composite foaming material and preparation method thereof | |
| CN111234327B (en) | Graphene natural rubber polymer composite foam material for soles of old people and preparation method thereof | |
| CN110511451A (en) | A kind of graphene arctic rubber polymeric composition and preparation method thereof | |
| KR20190047185A (en) | Graft copolymer, thermoplastic resin composition containing the same and method for preparing the thermoplastic resin | |
| CN110607000A (en) | Graphene natural rubber oil-resistant mixed foam material and preparation method thereof | |
| CN113004606A (en) | Wear-resistant EVA (ethylene vinyl acetate) foamed sole and processing technology thereof | |
| CN112250924A (en) | Formula and production process of environment-friendly recycled high-wear-resistance rubber and plastic material | |
| CN1218990C (en) | Preparation method of starch and polymer comosition | |
| CN101037495A (en) | Branching method of ethylene-acetic acid ethylene ester to maleic anhydride | |
| CN110922651A (en) | Graphene natural rubber polymer surfboard composite foam material and preparation method thereof | |
| CN103012972A (en) | Ethylene-propylene-diene monomer/nitrile rubber/organic montmorillonite oil resisting material and preparation method thereof | |
| CN1317324C (en) | Production of thermoplastic elastomer | |
| CN109679332A (en) | Flexible PA6 of a kind of low temperature resistant HI high impact height and preparation method thereof | |
| CN110885477A (en) | Graphene rubber high-molecular flame-retardant composite foam material and preparation method thereof | |
| CN111138726A (en) | Graphene natural rubber radiation-proof composite foam material and preparation method thereof | |
| CN105542085B (en) | A kind of grafting material of polybutene 1 and its application in the toughness reinforcing of nylon 6 | |
| CN110684245A (en) | Graphene natural rubber polymer static-control mixed foam material and preparation method thereof | |
| Sirisinha et al. | Changes in morphology and properties of NR–NBR blends. Effect of viscosity ratio modified by liquid natural rubber and epoxidised liquid natural rubber | |
| CN110922650A (en) | Graphene natural rubber polymer composite foam material for automobile seat cushion and preparation method thereof | |
| Neogi et al. | Threshold tensile strength and modulus of carbon-black-filled rubber vulcanizates | |
| CN113667257A (en) | Modified nano-cellulose/polypyrrole composite material and preparation method thereof, antistatic rubber composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200515 |