CN116606488B - Wear-resistant rubber-plastic composite material - Google Patents

Wear-resistant rubber-plastic composite material Download PDF

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CN116606488B
CN116606488B CN202310689074.XA CN202310689074A CN116606488B CN 116606488 B CN116606488 B CN 116606488B CN 202310689074 A CN202310689074 A CN 202310689074A CN 116606488 B CN116606488 B CN 116606488B
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rubber
stirring
reaction
wear
plastic composite
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CN116606488A (en
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唐树龙
陈剑鸣
熊岗
张善良
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Goodlife Technology Co ltd
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02Copolymers with acrylonitrile
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
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    • Y02T10/80Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86Optimisation of rolling resistance, e.g. weight reduction 

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Abstract

The invention discloses a wear-resistant rubber-plastic composite material, which belongs to the technical field of rubber-plastic composite materials and is prepared by the following steps: treating the aminated graphene oxide by an auxiliary agent to obtain an abrasion-resistant filler; mixing nitrile rubber, sulfur, N-isopropyl-N' -phenyl-p-phenylenediamine and tetramethylthiuram disulfide in an internal mixer to obtain a rubber base material; rubber base material, polyvinyl chloride, ternary polymerization nylon, dioctyl phthalate, wear-resistant filler and stearic acid are put into an internal mixer to be mixed, and then extruded and granulated to prepare the rubber-plastic composite material. According to the rubber-plastic composite material, the nitrile rubber and the polyvinyl chloride are used as matrix materials, and the graphene oxide treated by the auxiliary agent is added, so that the wear resistance can be improved; and the efficient flame retardant component can be introduced, so that the rubber and plastic material is endowed with safe, efficient, durable and stable flame retardant performance, and has very important application value.

Description

Wear-resistant rubber-plastic composite material
Technical Field
The invention belongs to the technical field of rubber and plastic composite materials, and particularly relates to a wear-resistant rubber and plastic composite material.
Background
The rubber and plastic material has the excellent performances of softness, bending resistance, cold resistance, heat resistance, flame retardance, water resistance, low heat conductivity coefficient, shock absorption, sound absorption and the like, and can be widely applied to industries of central air conditioners, buildings, chemical industry, vehicles, electric appliances and the like. As rubber and plastic materials are increasingly used in a variety of applications, the requirements for the properties of rubber and plastic are also increasing. In many applications, the rubber-plastic product has a relatively large corresponding friction force, for example, when the rubber-plastic composite material is applied to wire and cable sheathing materials, sealing strips, sports goods and the like, the rubber-plastic product is extremely easy to wear due to friction, so that the service life of the rubber-plastic product is generally not long.
Nitrile Butadiene Rubber (NBR) is used as the copolymer rubber of butadiene and acrylonitrile, and has the advantages of excellent oil resistance, aging resistance, wear resistance and the like. The NBR molecule has polar groups and better compatibility with polyvinyl chloride (PVC), so that the blend of the NBR molecule and the PVC has good mechanical properties, particularly has obvious modification effects on the defects of low impact strength, insufficient elasticity and the like of the PVC, and is used as a better raw material of wire and cable sheath materials, sealing strips, sports goods and the like. Compared with the common rubber products, the wear resistance of the rubber-plastic material is improved, but the wear resistance of the rubber-plastic material is still improved and improved due to the property of the nitrile rubber. In addition, the rubber and plastic material belongs to C-H substances, and has the defect of low flame retardant property, and the application of the rubber and plastic material is limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a wear-resistant rubber-plastic composite material.
According to the rubber-plastic composite material, the nitrile rubber and the polyvinyl chloride are used as the matrix material, so that the matrix material has better comprehensive performance, and the graphene oxide treated by the auxiliary agent is added, so that the graphene oxide can be uniformly dispersed in the matrix, higher thermal conductivity can be provided for the rubber-plastic material, a certain thermal conduction network is formed, the heat transfer generated by friction is facilitated in the friction process, the friction heat generation is reduced, the friction heat generation reduction is reflected in the improvement of the wear resistance, and the graphene oxide nano sheet has a certain self-lubricating effect, so that the wear resistance of the rubber nano composite material is improved; and the efficient flame retardant component can be introduced, so that the rubber and plastic material is endowed with safe, efficient, durable and stable flame retardant performance.
The aim of the invention can be achieved by the following technical scheme:
The wear-resistant rubber-plastic composite material comprises the following raw materials in parts by weight: 40-50 parts of nitrile rubber, 25-30 parts of polyvinyl chloride, 6-10 parts of ternary polymerization nylon, 8-10 parts of dioctyl phthalate, 12-15 parts of aminated graphene oxide, 4-6 parts of auxiliary agent, 0.8-1 part of stearic acid, 0.8-1 part of sulfur, 0.5-0.7 part of tetramethylthiuram disulfide and 1-1.2 parts of N-isopropyl-N' -phenyl p-phenylenediamine.
Further, the auxiliary agent is prepared by the following steps:
s1, uniformly mixing and stirring allyl diethyl phosphate, AIBN (azobisisobutyronitrile) and DMSO (dimethyl sulfoxide) according to a ratio of 1.78g to 0.23g to 10mL to obtain a reaction solution for later use; adding mercaptopropionic acid and DMSO into a four-neck flask with a stirring device, maintaining the temperature of the system at 70 ℃, dropwise adding a reaction solution under the stirring condition, reacting for 4 hours at 70 ℃ after the dropwise adding is finished, washing with a saturated saline solution and ethyl acetate system after the reaction is finished, taking an organic phase, drying with anhydrous Na 2SO4, filtering, and finally removing ethyl acetate by rotary evaporation to obtain an intermediate product 1; the ratio of the dosages of mercaptopropionic acid, DMSO and the reaction solution is 0.1mol:200mL:100mL;
Under the action of AIBN, unsaturated carbon-carbon double bond on allyl diethyl phosphate and thiol on mercaptopropionic acid molecule produce click reaction of mercapto-alkene, and the following chemical reaction process is carried out to obtain modifier;
S2, adding an intermediate product 1, triethylamine and anhydrous methylene dichloride into a dry three-neck flask provided with a stirring device, a condensing reflux device and a nitrogen guide pipe, introducing nitrogen, continuously introducing for 10min, adding a DMSO solution of melamine and DIC (N, N-diisopropylcarbodiimide, a dehydrating agent), stirring for reaction for 3h at room temperature under the protection of N 2 after the addition, extracting for three times with hot distilled water (the temperature is 60-70 ℃), taking an organic layer, drying anhydrous magnesium sulfate, filtering, and finally performing rotary evaporation (removing methylene dichloride) to obtain an intermediate product 2; the ratio of the amounts of intermediate 1, triethylamine, anhydrous dichloromethane, melamine, DIC was 28.4g:10.1g:300mL:0.105mol:12.6g; the concentration of the DMSO solution of the melamine is 2.1mol/L;
under the action of triethylamine and DIC, carrying out amidation reaction on-COOH on the molecule of the intermediate product 1 and-NH 2 on the molecule of melamine, and controlling the molar ratio of the-COOH to the molecule of melamine to be close to 1:1 and slightly excessive melamine, wherein under the influence of steric hindrance, only one-NH 2 of the melamine participates in the reaction to obtain the intermediate product 1, wherein the reaction process is as follows:
S3, placing the intermediate product 2 and methylene dichloride in a three-neck flask, keeping the temperature at 25-30 ℃, and stirring to completely dissolve the intermediate product 2 and the methylene dichloride; uniformly mixing 6-chloro-1-hexene, sodium carbonate and THF (tetrahydrofuran), slowly dripping the mixture into a three-neck flask by adopting a constant pressure dropping funnel, stirring while dripping, continuously stirring at 25-30 ℃ for reaction for 3 hours after dripping, removing most of solvents (dichloromethane and THF) by rotary evaporation after the reaction is finished, adding distilled water, uniformly mixing, extracting by using dichloromethane, washing an organic phase for a plurality of times by using saturated NaCl aqueous solution, drying by using anhydrous Na 2SO4, carrying out suction filtration, and finally carrying out reduced pressure distillation to remove dichloromethane to obtain an intermediate product 3; the ratio of the amounts of intermediate 2, 6-chloro-1-hexene and sodium carbonate was 9.8g:0.11mol:10.6g;
Under the action of sodium carbonate, nucleophilic substitution reaction is carried out on-NH 2 on the molecule of the intermediate product 2 and-Cl on the molecule of 6-chloro-1-hexene, and the following chemical reaction is carried out by controlling the molar ratio of the two to be close to 1:4, so as to obtain an intermediate product 3:
S4, adding the intermediate product 3, AIBN and DMSO into a four-neck flask with a stirring device, stirring and dissolving uniformly, heating and heating, dripping DMSO solution of mercaptopropionic acid into the system when the temperature is stabilized at 75 ℃, reacting for 4 hours at 75 ℃, washing with saturated saline water and dichloromethane after the reaction is finished, taking an organic phase, removing the dichloromethane by rotary evaporation, separating by a silica gel column (eluent is a mixed solution of n-hexane/ethyl acetate=4:1), and distilling under reduced pressure to obtain an auxiliary agent; the ratio of the amounts of intermediate 3, AIBN and mercaptopropionic acid was 7.6g:2.8g:0.01mol; the concentration of DMSO solution of mercaptopropionic acid is 1mol/L;
Under AIBN catalysis, unsaturated carbon-carbon double bond contained in the intermediate product 3 molecule and mercapto on mercaptopropionic acid molecule undergo click reaction, and only one-C=C-on the intermediate product 3 participates in the reaction by controlling the molar ratio of the unsaturated carbon-carbon double bond to the mercapto on mercaptopropionic acid molecule to be close to 1:1 and slightly excessive intermediate product 3, wherein the reaction process is as follows, so as to obtain an auxiliary agent:
further, the rubber-plastic composite material is prepared by the following steps:
Firstly, adding aminated graphene oxide and DMF (N, N-dimethylformamide) into a three-neck flask with a stirring device, mechanically stirring for 1h at room temperature, adding an auxiliary agent into the system, continuously stirring for 30min, then adding EDC-HCl (1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and a coupling agent), transferring the mixed solution into a water bath at 60 ℃ for continuously stirring and reacting for 4h, centrifugally separating after the reaction is finished, sequentially washing with DMF and ethanol water solution (volume fraction of 50%) for 4-5 times respectively, and finally, fully drying and grinding the product in a vacuum oven at 80 ℃ to obtain the wear-resistant filler; the-COOH contained on the auxiliary agent molecule and the-NH 2 on the surface of the aminated graphene oxide are subjected to chemical reaction to form the wear-resistant filler;
secondly, putting nitrile rubber, sulfur, N-isopropyl-N' -phenyl-p-phenylenediamine and tetramethylthiuram disulfide into an internal mixer, mixing for 20-25min at the temperature of 150-160 ℃, discharging and obtaining a rubber base material;
And thirdly, adding the rubber base material, polyvinyl chloride, ternary polymerization nylon, dioctyl phthalate, wear-resistant filler and stearic acid into an internal mixer, mixing for 20-30min at 170-180 ℃, and then feeding the mixture into a double-stage screw extruder through a double-cone mixer for mixing, extruding and granulating to obtain the rubber-plastic composite material.
Further, EDC-HCl is used in an amount of 8% of the mass of the aminated graphene oxide.
The formed wear-resistant filler takes graphene oxide as a matrix and takes an organic layer formed by auxiliary agent molecules as a surface layer, the formation of the organic layer can improve the interfacial compatibility between the graphene oxide and a rubber matrix and promote the dispersion of the graphene oxide, and in addition, the auxiliary agent molecules contain a plurality of fatty chains, and the fatty chains have higher flexibility and higher similar compatibility with the rubber molecular chains, so that the uniform dispersion of the graphene oxide in the rubber material can be further promoted; the uniformly dispersed graphene oxide can provide higher thermal conductivity for rubber and plastic materials to form a certain thermal conduction network, so that heat transfer generated by friction is facilitated in the friction process, friction heat generation is reduced, the reduction of the friction heat generation is reflected on the improvement of wear resistance, and the graphene oxide nano-sheets have a certain self-lubricating effect, so that the wear resistance of the rubber nano-composite material is improved;
In addition, the auxiliary agent molecules contain fatty chains distributed in a dendritic manner, and the tail ends of the fatty chains contain unsaturated carbon-carbon double bonds, so that the auxiliary agent can participate in the crosslinking process in the banburying process of the rubber and plastic material, the formation of a crosslinked network structure in the rubber and plastic material is promoted, the crosslinking density is improved, the compactness of the material is improved, and the wear resistance of the rubber and plastic material is further improved;
The auxiliary agent molecule contains N-containing heterotomic ring, phosphate group and S-containing group, belongs to N-P-S synergistic flame retardant components, has a multi-effect flame retardant mechanism, can endow the rubber and plastic material with high-efficiency and safe flame retardant performance, has chemical acting force with a matrix, is difficult to migrate and exude, and has flame retardant durability.
Further, the aminated graphene oxide is prepared by the following steps:
Adding graphene oxide into a three-neck flask filled with DMF, mechanically stirring for 1h at room temperature, adding ethylenediamine into the system, continuously stirring for 1h, then adding EDC-HCl, transferring the mixed solution into a water bath at 60 ℃ for continuous stirring, installing a reflux condensing device for reaction for 6h, centrifugally separating after the reaction is finished, washing for 4-5 times with absolute ethyl alcohol (to remove unreacted ethylenediamine), finally drying in vacuum, and grinding to obtain the aminated graphene oxide; the ratio of graphene oxide, DMF, ethylenediamine, EDC-HCl was 1 g/100 mL/0.6 g/50 mg.
The surface of the graphene oxide contains more oxygen-containing groups (-OH, epoxy groups and-COOH), the-COOH is subjected to condensation reaction with-NH 2 on ethylenediamine molecules under the action of EDC-HCl (carbonyl activating reagent), and the-NH 2 is introduced into the surface of the graphene oxide, so that the aminated graphene oxide is obtained.
The invention has the beneficial effects that:
According to the rubber-plastic composite material, the nitrile rubber and the polyvinyl chloride are used as the matrix material, so that the matrix material has better comprehensive performance, and the graphene oxide treated by the auxiliary agent is added, so that the graphene oxide can be uniformly dispersed in the matrix, higher thermal conductivity can be provided for the rubber-plastic material, a certain thermal conduction network is formed, the heat transfer generated by friction is facilitated in the friction process, the friction heat generation is reduced, the friction heat generation reduction is reflected in the improvement of the wear resistance, and the graphene oxide nano sheet has a certain self-lubricating effect, so that the wear resistance of the rubber nano composite material is improved; and the efficient flame retardant component can be introduced, so that the rubber and plastic material is endowed with safe, efficient, durable and stable flame retardant performance, and has very important application value.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparing aminated graphene oxide:
Adding 10g of graphene oxide into a three-neck flask filled with 1000mL of DMF, mechanically stirring at room temperature for 1h, adding 6g of ethylenediamine into the system, continuously stirring for 1h, then adding 0.5g of EDC-HCl, transferring the mixed solution into a water bath at 60 ℃ for continuously stirring, installing a reflux condensing device for reaction for 6h, centrifugally separating after the reaction is finished, washing with absolute ethyl alcohol for 5 times (to remove unreacted ethylenediamine), and finally drying in vacuum and grinding to obtain the aminated graphene oxide.
Example 2
Preparing an auxiliary agent:
S1, mixing and stirring 17.8g of diethyl allyl phosphate, 2.3g of AIBN and 100mL of DMSO uniformly to obtain a reaction solution for later use; adding 0.1mol of mercaptopropionic acid and 200mL of DMSO into a four-neck flask with a stirring device, maintaining the temperature of the system at 70 ℃, dropwise adding 100mL of reaction solution under the stirring condition, reacting for 4 hours at 70 ℃ after the dropwise addition, washing with a saturated saline solution and ethyl acetate system after the reaction is finished, taking an organic phase, drying with anhydrous Na 2SO4, filtering, and finally removing ethyl acetate by rotary evaporation to obtain an intermediate product 1;
S2, adding 28.4g of intermediate 1, 10.1g of triethylamine and 300mL of anhydrous dichloromethane into a dry three-neck flask provided with a stirring device, a condensing reflux device and a nitrogen guide pipe, introducing nitrogen, continuously introducing 10min, adding 50mL of melamine DMSO solution (with the concentration of 2.1 mol/L) and 12.6g of DIC, stirring and reacting for 3h under the protection of N 2 after the addition, extracting three times with hot distilled water (with the temperature of 60 ℃) after the reaction is finished, taking an organic layer, drying the organic layer with anhydrous magnesium sulfate, filtering, and finally performing rotary evaporation (removing dichloromethane) to obtain an intermediate 2;
S3, placing 9.8g of the intermediate product 2 and 100mL of dichloromethane in a three-neck flask, keeping the temperature at 25 ℃, and stirring to completely dissolve the intermediate product 2; uniformly mixing 0.11mol of 6-chloro-1-hexene, 10.6g of sodium carbonate and 40mL of THF, slowly dripping the mixture into a three-neck flask by adopting a constant pressure dropping funnel, stirring while dripping, continuously stirring at 25 ℃ for 3 hours after dripping, removing most of solvents (dichloromethane and THF) by rotary evaporation after the reaction is finished, adding distilled water, uniformly mixing, extracting by using dichloromethane, washing an organic phase for a plurality of times by using saturated NaCl aqueous solution, drying by using anhydrous Na 2SO4, carrying out suction filtration, and finally removing dichloromethane by reduced pressure distillation to obtain an intermediate product 3;
s4, adding 7.6g of intermediate 3, 2.8g of AIBN and 50mL of DMSO into a four-necked flask with a stirring device, heating while stirring and dissolving uniformly, dropwise adding 10mL of DMSO solution of mercaptopropionic acid (the concentration is 1 mol/L) into the system when the temperature is stabilized at 75 ℃, reacting for 4 hours at 75 ℃ after the dropwise addition, washing with saturated saline and dichloromethane after the reaction is finished, taking an organic phase, separating by a silica gel column (eluent is a mixed solution of n-hexane/ethyl acetate=4:1), and distilling under reduced pressure to obtain the auxiliary agent.
Example 3
Preparing an auxiliary agent:
S1, mixing and stirring 35.6g of diethyl allyl phosphate, 4.6g of AIBN and 200mL of DMSO uniformly to obtain a reaction solution for later use; adding 0.2mol of mercaptopropionic acid and 400mL of DMSO into a four-neck flask with a stirring device, maintaining the temperature of the system at 70 ℃, dropwise adding 200mL of reaction solution under the stirring condition, reacting for 4 hours at 70 ℃ after the dropwise addition, washing with a saturated saline solution and ethyl acetate system after the reaction is finished, taking an organic phase, drying with anhydrous Na 2SO4, filtering, and finally removing ethyl acetate by rotary evaporation to obtain an intermediate product 1;
S2, adding 56.8g of an intermediate product 1, 20.2g of triethylamine and 600mL of anhydrous dichloromethane into a dry three-neck flask provided with a stirring device, a condensing reflux device and a nitrogen guide pipe, introducing nitrogen, continuously introducing 10min, adding 100mL of a DMSO solution of melamine (with the concentration of 2.1 mol/L) and 25.2g of DIC, stirring and reacting for 3h under the protection of N 2 after the addition, extracting three times with hot distilled water (with the temperature of 70 ℃) after the reaction is finished, taking an organic layer, drying the organic layer with anhydrous magnesium sulfate, filtering, and finally performing rotary evaporation (removing dichloromethane) to obtain an intermediate product 2;
S3, placing 19.6g of the intermediate 2 and 200mL of dichloromethane in a three-neck flask, keeping the temperature at 30 ℃, and stirring to completely dissolve the intermediate 2; uniformly mixing 0.22mol of 6-chloro-1-hexene, 21.2g of sodium carbonate and 80mL of THF, slowly dripping the mixture into a three-neck flask by adopting a constant pressure dropping funnel, stirring while dripping, continuously stirring at 30 ℃ for 3 hours after dripping, removing most of solvents (dichloromethane and THF) by rotary evaporation after the reaction is finished, adding distilled water, uniformly mixing, extracting by using dichloromethane, washing an organic phase for a plurality of times by using saturated NaCl aqueous solution, drying by using anhydrous Na 2SO4, carrying out suction filtration, and finally removing dichloromethane by reduced pressure distillation to obtain an intermediate product 3;
S4, adding 15.2g of intermediate 3, 5.6g of AIBN and 100mL of DMSO into a four-necked flask with a stirring device, heating while stirring and dissolving uniformly, dropwise adding 20mL of DMSO solution of mercaptopropionic acid (the concentration is 1 mol/L) into the system when the temperature is stabilized at 75 ℃, reacting for 4 hours at 75 ℃ after the dropwise addition is finished, washing with saturated saline and dichloromethane after the reaction is finished, taking an organic phase, separating by a silica gel column (eluent is a mixed solution of n-hexane/ethyl acetate=4:1), and distilling under reduced pressure to obtain the auxiliary agent.
Example 4
Preparing a rubber-plastic composite material:
Firstly, adding 120g of the aminated graphene oxide prepared in the example 1 and 1.5L of DMF into a three-neck flask with a stirring device, mechanically stirring for 1h at room temperature, adding 40g of the auxiliary agent prepared in the example 2 into the system, continuously stirring for 30min, then adding 9.6g of EDC-HCl, transferring the mixed solution into a water bath at 60 ℃ for continuously stirring and reacting for 4h, centrifuging after the reaction is finished, washing for 4 times by using DMF and ethanol water solution (volume fraction 50%) respectively, and finally, fully drying and grinding the product in a vacuum oven at 80 ℃ to obtain the wear-resistant filler;
Secondly, putting 400g of nitrile rubber, 8g of sulfur, 10g of N-isopropyl-N' -phenyl-p-phenylenediamine and 5g of tetramethylthiuram disulfide into an internal mixer, mixing for 20min at the temperature of 150 ℃, discharging and obtaining a rubber base material;
And thirdly, adding the rubber base material, 250g of polyvinyl chloride, 60g of ternary polymerization nylon, 80g of dioctyl phthalate, wear-resistant filler and 8g of stearic acid into an internal mixer, mixing at 170 ℃ for 20min, and then feeding the mixture into a double-stage screw extruder through a double-cone mixer for mixing, extruding and granulating to obtain the rubber-plastic composite material.
Example 5
Preparing a rubber-plastic composite material:
Firstly, 135g of the aminated graphene oxide prepared in the example 1 and 1.8L of DMF are added into a three-neck flask with a stirring device, after mechanical stirring is carried out for 1h at room temperature, 50g of the auxiliary agent prepared in the example 3 is added into a system, stirring is continued for 30min, then 10.8g of EDC-HCl is added, the mixed solution is transferred into a water bath with the temperature of 60 ℃ for continuing stirring reaction for 4h, after the reaction is finished, centrifugal separation is carried out, and DMF and ethanol aqueous solution (volume fraction 50%) are sequentially used for washing for 5 times respectively, finally, the product is fully dried in a vacuum oven with the temperature of 80 ℃ and ground, thus obtaining the wear-resistant filler;
secondly, putting 450g of nitrile rubber, 9g of sulfur, 11g of N-isopropyl-N' -phenyl-p-phenylenediamine and 6g of tetramethylthiuram disulfide into an internal mixer, mixing for 23min at 155 ℃, discharging and obtaining a rubber base material;
And thirdly, adding the rubber base material, 280g of polyvinyl chloride, 80g of ternary polymerization nylon, 90g of dioctyl phthalate, the wear-resistant filler and 9g of stearic acid into an internal mixer, mixing at 175 ℃ for 25min, and then feeding the mixture into a double-stage screw extruder through a double-cone mixer for mixing, extruding and granulating to obtain the rubber-plastic composite material.
Example 6
Preparing a rubber-plastic composite material:
Firstly, 150g of the aminated graphene oxide prepared in the example 1 and 2L of DMF are added into a three-neck flask with a stirring device, after mechanical stirring is carried out for 1h at room temperature, 60g of the auxiliary agent prepared in the example 2 is added into a system, stirring is continued for 30min, then 12g of EDC-HCl is added, the mixed solution is transferred into a water bath at 60 ℃ for continuous stirring reaction for 4h, after the reaction is finished, centrifugal separation is carried out, DMF and ethanol aqueous solution (volume fraction 50%) are sequentially used for washing for 5 times respectively, finally, the product is fully dried in a vacuum oven at 80 ℃, and grinding is carried out, thus obtaining the wear-resistant filler;
Secondly, putting 500g of nitrile rubber, 10g of sulfur, 12g of N-isopropyl-N' -phenyl-p-phenylenediamine and 7g of tetramethylthiuram disulfide into an internal mixer, mixing for 25min at 160 ℃, discharging and obtaining a rubber base material;
And thirdly, adding the rubber base material, 300g of polyvinyl chloride, 100g of ternary polymerization nylon, 100g of dioctyl phthalate, wear-resistant filler and 10g of stearic acid into an internal mixer, mixing at 180 ℃ for 30min, and then feeding the mixture into a double-stage screw extruder through a double-cone mixer for mixing, extruding and granulating to obtain the rubber-plastic composite material.
Comparative example
The auxiliary raw material in the example 4 is removed, and the rest raw materials and the preparation process are unchanged to obtain the rubber-plastic composite material.
The rubber and plastic composites obtained in examples 4-6 and comparative examples were processed and cut into test samples and subjected to the following performance tests:
the tensile properties of the materials were tested according to GB/T528-1998;
An Aldrich abrasion tester is adopted to test the abrasion volume of a sample running 1.61 km;
Flame retardant rating according to UL94-V0 standard:
The results are shown in the following table:
As can be seen from the data in the table, the rubber-plastic composite material obtained by the invention has good mechanical property and flame retardant property and high wear resistance; the data of the comparative example show that the addition of the auxiliary agent not only can greatly improve the flame retardant property and the wear resistance of the material, but also can improve the mechanical property of the material to a certain extent.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.

Claims (6)

1. The wear-resistant rubber-plastic composite material is characterized by being prepared by the following steps:
Firstly, adding the aminated graphene oxide and DMF into a three-neck flask with a stirring device, mechanically stirring for 1h at room temperature, adding an auxiliary agent into the system, continuously stirring for 30min, then adding EDC-HCl, transferring the mixed solution into a water bath at 60 ℃ for continuously stirring and reacting for 4h, after the reaction is finished, centrifugally separating, sequentially washing with DMF and ethanol water solution for 4-5 times respectively, and finally, fully drying and grinding the product in a vacuum oven at 80 ℃ to obtain the wear-resistant filler;
Secondly, putting nitrile rubber, sulfur, N-isopropyl-N' -phenyl-p-phenylenediamine and tetramethylthiuram disulfide into an internal mixer, mixing for 20-25min at the temperature of 150-160 ℃, and discharging to obtain a rubber base material;
thirdly, adding the rubber base material, polyvinyl chloride, ternary polymerization nylon, dioctyl phthalate, wear-resistant filler and stearic acid into an internal mixer, mixing for 20-30min at 170-180 ℃, and then feeding the mixture into a double-stage screw extruder through a double-cone mixer to carry out mixing extrusion granulation to obtain the rubber-plastic composite material;
The auxiliary agent is prepared through the following steps:
S1, uniformly mixing and stirring allyl diethyl phosphate, AIBN and DMSO according to a ratio of 1.78g to 0.23g to 10mL to obtain a reaction solution for later use; adding mercaptopropionic acid and DMSO into a four-neck flask with a stirring device, maintaining the temperature of the system at 70 ℃, dropwise adding a reaction solution under the stirring condition, reacting for 4 hours at 70 ℃ after the dropwise adding is finished, washing with a saturated saline water and ethyl acetate system after the reaction is finished, taking an organic phase, drying with anhydrous Na 2SO4, filtering, and finally removing ethyl acetate by rotary evaporation to obtain an intermediate product 1, wherein the structural formula is as follows:
S2, adding an intermediate product 1, triethylamine and anhydrous dichloromethane into a dry three-neck flask provided with a stirring device, a condensing reflux device and a nitrogen guide pipe, introducing nitrogen, continuously introducing for 10min, adding a DMSO solution of melamine and DIC, stirring and reacting for 3h at room temperature under the protection of N 2 after the addition, extracting for three times by using hot distilled water after the reaction is finished, taking an organic layer, drying by using anhydrous magnesium sulfate, filtering, and finally performing rotary evaporation to obtain an intermediate product 2, wherein the structural formula is as follows:
S3, placing the intermediate product 2 and methylene dichloride in a three-neck flask, keeping the temperature at 25-30 ℃, and stirring to completely dissolve the intermediate product 2 and the methylene dichloride; after evenly mixing 6-chloro-1-hexene, sodium carbonate and THF, slowly dripping the mixture into a three-neck flask by adopting a constant pressure dropping funnel, stirring while dripping, continuously stirring at 25-30 ℃ for reaction for 3 hours after dripping, removing most of solvent by rotary evaporation after the reaction is finished, adding distilled water for evenly mixing, then extracting by using dichloromethane, washing an organic phase for a plurality of times by using saturated NaCl aqueous solution, drying by using anhydrous Na 2SO4, carrying out suction filtration, and finally removing dichloromethane by reduced pressure distillation to obtain an intermediate product 3, wherein the structural formula is as follows:
S4, adding the intermediate product 3, AIBN and DMSO into a four-neck flask with a stirring device, heating while stirring and dissolving uniformly, dropwise adding a DMSO solution of mercaptopropionic acid into the system when the temperature is stabilized at 75 ℃, reacting for 4 hours at 75 ℃, washing with saturated saline water and dichloromethane after the reaction is finished, taking an organic phase, removing the dichloromethane by rotary evaporation, separating by a silica gel column, and distilling under reduced pressure to obtain an auxiliary agent, wherein the structural formula is as follows:
2. the wear-resistant rubber-plastic composite material according to claim 1, wherein the EDC-HCl is 8% of the mass of the aminated graphene oxide in the first step.
3. The wear-resistant rubber-plastic composite material according to claim 1, which is characterized by comprising the following raw materials in parts by weight: 40-50 parts of nitrile rubber, 25-30 parts of polyvinyl chloride, 6-10 parts of ternary polymerization nylon, 8-10 parts of dioctyl phthalate, 12-15 parts of aminated graphene oxide, 4-6 parts of auxiliary agent, 0.8-1 part of stearic acid, 0.8-1 part of sulfur, 0.5-0.7 part of tetramethylthiuram disulfide and 1-1.2 parts of N-isopropyl-N' -phenyl p-phenylenediamine.
4. The wear-resistant rubber-plastic composite material according to claim 1, wherein the ratio of the amounts of mercaptopropionic acid, DMSO and the reaction solution in the step S1 is 0.1mol:200mL:100mL;
The ratio of the amounts of intermediate 1, triethylamine, anhydrous dichloromethane, melamine, DIC in step S2 was 28.4g:10.1g:300mL:0.105mol:12.6g; the concentration of the DMSO solution of the melamine is 2.1mol/L;
the ratio of the amounts of intermediate 2, 6-chloro-1-hexene and sodium carbonate used in step S3 was 9.8g:0.11mol:10.6g;
The ratio of the amounts of intermediate 3, AIBN and mercaptopropionic acid used in step S4 was 7.6g:2.8g:0.01mol; the concentration of the DMSO solution of mercaptopropionic acid is 1mol/L.
5. The wear-resistant rubber-plastic composite material according to claim 1, wherein the aminated graphene oxide is prepared by the following steps:
Adding graphene oxide into a three-neck flask filled with DMF, mechanically stirring for 1h at room temperature, adding ethylenediamine into the system, continuously stirring for 1h, then adding EDC-HCl, transferring the mixed solution into a water bath with the temperature of 60 ℃ for continuous stirring, installing a reflux condensing device for reaction for 6h, centrifugally separating after the reaction is finished, washing for 4-5 times with absolute ethyl alcohol, finally drying in vacuum, and grinding to obtain the aminated graphene oxide.
6. The wear-resistant rubber-plastic composite material according to claim 5, wherein the dosage ratio of graphene oxide, DMF, ethylenediamine and EDC-HCl is 1g to 100mL to 0.6g to 50mg.
CN202310689074.XA 2023-06-12 2023-06-12 Wear-resistant rubber-plastic composite material Active CN116606488B (en)

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