CN112852181A - High-strength wear-resistant wood-plastic composite material and preparation method thereof - Google Patents

High-strength wear-resistant wood-plastic composite material and preparation method thereof Download PDF

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CN112852181A
CN112852181A CN202110037031.4A CN202110037031A CN112852181A CN 112852181 A CN112852181 A CN 112852181A CN 202110037031 A CN202110037031 A CN 202110037031A CN 112852181 A CN112852181 A CN 112852181A
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sawdust
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王诗英
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/085—Copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—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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Abstract

The invention relates to a high-strength wear-resistant wood-plastic composite material and a preparation method thereof, belonging to the technical field of preparation of polymer composite materials. According to the invention, the processed sawdust, the self-made wear-resistant particles and the corresponding plastic wear-resistant reinforcing material are added into the wood-plastic composite material, so that the wear resistance and the mechanical property of the wood-plastic composite material are greatly improved, the application range of the wood-plastic composite material is widened, and the wood-plastic composite material has a wide application prospect.

Description

High-strength wear-resistant wood-plastic composite material and preparation method thereof
Technical Field
The invention relates to a high-strength wear-resistant wood-plastic composite material and a preparation method thereof, belonging to the technical field of preparation of polymer composite materials.
Background
In recent years, relevant scholars in China do a lot of work on the aspect of performance research of the wood-plastic composite material, and some valuable research results are obtained. The wood-plastic composite material is a new type composite material which is made up by using thermoplastic plastics of polyethylene, polypropylene and polyvinyl chloride, etc. instead of resin adhesive and mixing them with a certain quantity of waste plant fibres of wood flour, rice husk and straw, and making them pass through the processes of extrusion, die pressing and injection moulding so as to obtain the invented plate material or section material, which is an excellent substitute for natural wood. The wood-plastic composite material has the characteristics of wood and plastic, has good dimensional stability, can fully utilize waste plant fiber and waste plastic, and reduces environmental pollution, so the wood-plastic composite material is widely applied to indoor decoration and outdoor use.
The plant fiber is polar substance, the surface of the plant fiber contains a large amount of hydroxyl, while the plastic (such as PE and PP) is non-polar substance, the interface compatibility with the plant fiber is poor, and a compatilizer (such as maleic anhydride grafted PE) is generally added to improve the interface compatibility. The compatilizer generally contains macromolecular polymers of polar groups (such as anhydride groups and carboxyl groups), the polar groups can generate esterification reaction with hydroxyl on the surface of the plant fiber, and macromolecular chains of the compatilizer have quite good compatibility with thermoplastic plastics, so that the interface compatibility between the plant fiber and the plastics is improved.
At present, almost all raw materials such as a compatilizer, a lubricant, a pigment and the like are added into a high-speed mixer at the same time and uniformly mixed, then plasticizing and granulating are directly carried out by a parallel double-screw extruder, and the mixture is extruded and molded by a conical double-screw extruder. The strength and the abrasion resistance of the wood-plastic composite material are lower, so that the application range of the wood-plastic composite material is limited.
In view of the above defects, the designer actively makes research and innovation to create a high-strength wear-resistant wood-plastic composite material and a preparation method thereof, so that the high-strength wear-resistant wood-plastic composite material has industrial utilization value.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a high-strength wear-resistant wood-plastic composite material and a preparation method thereof.
The invention relates to a high-strength wear-resistant wood-plastic composite material which comprises the following raw materials in parts by weight:
70-80 parts of waste plastic;
treating 10-20 parts of sawdust;
10-15 parts of straw;
1-3 parts of an auxiliary agent;
2-5 parts of a lubricant;
the processed sawdust is prepared by immersing sawdust in water and freezing with liquid nitrogen.
Further, 8-10 parts by weight of self-made anti-wear particles are also included;
the self-made anti-wear particles are prepared by the reaction of copper sulfate solution, coconut oil fatty acid diethanolamide, hydrochloric acid solution and polytetrafluoroethylene.
Further, the plastic wear-resistant reinforcing material also comprises 5-15 parts by weight of plastic wear-resistant reinforcing material;
the plastic anti-wear reinforcing material is prepared by reacting sodium silicate solution, hydrochloric acid, mussel mucin and catechol oxidase.
A preparation method of a high-strength wear-resistant wood-plastic composite material comprises the following specific preparation steps:
(1) weighing 70-80 parts of waste plastics, 10-20 parts of treated sawdust, 10-15 parts of straws, 5-15 parts of plastic wear-resistant reinforcing materials, 8-10 parts of self-made wear-resistant particles, 1-3 parts of auxiliaries and 2-5 parts of lubricants in parts by weight;
(2) putting the waste plastics into a mixing roll for stirring and mixing, stopping when mixing is sufficient, adding the plastic anti-wear reinforcing material and the self-made anti-wear particles, and continuously mixing fully to obtain modified plastics;
(3) putting the modified plastic and the processed sawdust into a mixing roll, mixing for 5-20 min, stirring at a rotating speed of 200-700 r/min, adding an auxiliary agent, and stirring to obtain a prefabricated product, wherein the mixing roll adopts a W-shaped cylinder body and is provided with a sleeve-shaped device, so that the gap between a stirring paddle and the cylinder wall is consistent, and the stirring effect is optimal;
(4) mixing the prefabricated object with a lubricant, and continuously stirring and heating to 100-300 ℃ to form a fluid mixture;
(5) and adding the mixture into a single-screw extruder, and extruding by using the single-screw extruder to obtain the high-strength wear-resistant wood-plastic composite material.
Further, the preparation steps of the processed wood chips are as follows:
weighing sawdust, soaking the sawdust in deionized water for 15-20 h, taking out the soaked sawdust, immediately spraying and freezing the sawdust with liquid nitrogen for 2-3 min, heating to 40-50 ℃ after spraying, thawing for 10-15 min, and repeatedly freezing and thawing for 5-8 times to obtain the treated sawdust.
Further, the preparation steps of the self-made anti-wear particles are as follows:
(1) mixing a copper sulfate solution with the mass fraction of 30% and coconut oil fatty acid diethanolamide according to the mass ratio of 10:1, putting the mixture into an ultrasonic oscillator, and carrying out ultrasonic oscillation treatment for 15-20 min at the frequency of 30-40 kHz to obtain a microemulsion;
(2) heating the microemulsion to 40-50 ℃, putting the microemulsion into an electrodeposition device, and keeping the current density at 0.05-0.2A/cm2Carrying out electrodeposition treatment for 20-30 min under the condition that the distance between the polar plates is 10-20 mm, carrying out centrifugal separation on the microemulsion subjected to electrodeposition treatment to obtain filter residues, and carrying out vacuum drying to obtain the nano copper powder;
(3) putting the obtained nano copper powder into a hydrochloric acid solution with the mass fraction of 6%, performing dealloying corrosion treatment for 8-11 h to obtain modified nano copper powder after the treatment is finished, mixing the modified nano copper powder and polytetrafluoroethylene according to the mass ratio of 1:10, putting the mixture into an internal mixer, internally mixing the mixture at 300-320 ℃ for 1-2 h, and extruding and granulating the mixture through a screw extruder to obtain the self-made wear-resistant particles.
Further, the preparation steps of the plastic anti-wear reinforcing material are as follows:
(1) weighing sawdust, soaking the sawdust in deionized water for 15-20 h, taking out the soaked sawdust, immediately spraying and freezing the sawdust with liquid nitrogen for 2-3 min, heating to 40-50 ℃ after spraying, thawing for 10-15 min, and repeatedly freezing and thawing for 5-8 times to obtain treated sawdust;
(2) pouring a sodium silicate solution with the concentration of 0.5mol/L into a beaker, adjusting the pH to 6.0 by using hydrochloric acid with the concentration of 1mol/L, stirring and reacting for 1-2 h by using a magnetic stirrer at the rotating speed of 300-400 r/min, moving into a reaction kettle after the reaction is finished, heating to the temperature of 150-200 ℃, and carrying out thermal insulation hydrolysis reaction for 2-3 h to obtain self-prepared silica sol;
(3) mixing the obtained silica sol and mussel mucin according to the mass ratio of 10:1 to obtain a mixed solution, dripping ammonia water into the mixed solution to adjust the pH value to 8, heating to 35-45 ℃, standing for reaction for 3-5 h, then continuously adding catechol oxidase accounting for 5% of the mass of the mixed solution, and continuously standing for reaction for 6-8 h to obtain the plastic anti-wear reinforcing material.
Further, in the step (2), the waste plastic is any one of a waste film, a plastic bag, a plastic express bag, a plastic bottle and a plastic sheet.
Further, the assistant in the step (3) is any one of a silane coupling agent, a titanate coupling agent or an aluminate coupling agent.
Further, the power of the single-screw extruder in the step (5) is 0.75KW, and a cycloidal pin gear speed reducing motor is used.
By the scheme, the invention at least has the following advantages:
(1) the high-strength wear-resistant wood-plastic composite material disclosed by the invention widens the pore structure of the sawdust through repeated freeze thawing treatment, so that the specific surface area of the sawdust is increased, the contact probability of the sawdust and plastic can be increased, the compatibility of the sawdust and the plastic is improved, the cohesion of the plastic-wood pallet is improved, and the mechanical strength of the plastic-wood pallet is increased;
(2) by utilizing that 10% of dopa groups exist in mussel mucin peptide chain fragments, some phenolic hydroxyl groups in the dopa groups are oxidized into quinone under the condition of higher pH value, the process can be accelerated in the presence of catechol oxidase, the oxidized dopa and unoxidized dopa are crosslinked to form a high-molecular reticular polymer which is attached to the surface of nano silica in silica sol, so that the surface of the inorganic silica is polymerized and materialized, and the high-molecular reticular polymer is used as a transition layer to increase the compatibility between the inorganic silica and a plastic polymer, further improve the cohesive force of a plastic-wood tray and increase the mechanical strength of the plastic-wood tray, and the inorganic characteristics of the nano silica form a physical nano self-assembly barrier through the self-assembly and crosslinking of nano particles, so that the mechanical property of the whole plastic-wood material can be improved, the mechanical strength is enhanced, and in addition, the ball bearing effect of the nano silica self-assembly barrier is realized, the wear-resistant and wear-reducing capacity of the wood-plastic composite material can be improved, internal energy consumption caused by the wear of the wood-plastic composite material is reduced through rolling sliding among particles, the wear-resistant effect of the material is further improved, and the nano silicon dioxide particles can also fill dents on the wear surface, so that the subsequent friction is reduced, and the wear-resistant performance of the wood-plastic composite material is further improved;
(3) the polytetrafluoroethylene is mainly composed of a cylindrical shell which is completely surrounded by fluorine atoms and is composed of a carbon-carbon main chain spiral structure, the cylindrical structure enables the attraction among polytetrafluoroethylene molecules to be very weak so as to be easy to slide, therefore, when the polytetrafluoroethylene is subjected to external friction stress, the internal wear energy consumption of the material can be weakened through the intermolecular sliding, so that the wear resistance of the material is improved, on one hand, the surface of the porous nano copper dioxide particles in the polytetrafluoroethylene is rough, the friction coefficient of the material can be increased, the wear resistance of the material is further improved, on the other hand, the pore structure of the rough nano copper powder particles can be used as a physical anchoring point combined with a polymer material, the internal bonding force between the porous nano copper dioxide particles and the polymer material is increased, so that the cohesion and the cohesion of the wood-plastic material are improved, and the mechanical property of the wood-plastic material is effectively improved, and the porous copper nano particles can also fill the dents on the wear surface, thereby reducing friction, improving the wear resistance of the wood-plastic material again and having wide application prospect.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The preparation method of the high-strength wear-resistant wood-plastic composite material in the preferred embodiment of the invention comprises the following steps:
(1) and (3) wood chip treatment:
weighing sawdust, soaking the sawdust in deionized water for 15-20 h, taking out the soaked sawdust, immediately spraying and freezing the sawdust with liquid nitrogen for 2-3 min, heating to 40-50 ℃ after spraying, thawing for 10-15 min, and repeatedly freezing and thawing for 5-8 times to obtain treated sawdust; through repeated freeze thawing treatment, the pore structure of the sawdust is widened, the specific surface area of the sawdust is increased, the contact probability of the sawdust and the plastic can be increased, the compatibility of the sawdust and the plastic is improved, the cohesion of the plastic-wood tray is improved, and the mechanical strength of the plastic-wood tray is increased;
(2) pouring a sodium silicate solution with the concentration of 0.5mol/L into a beaker, adjusting the pH to 6.0 by using hydrochloric acid with the concentration of 1mol/L, stirring and reacting for 1-2 h by using a magnetic stirrer at the rotating speed of 300-400 r/min, moving into a reaction kettle after the reaction is finished, heating to the temperature of 150-200 ℃, and carrying out thermal insulation hydrolysis reaction for 2-3 h to obtain self-prepared silica sol; firstly, sodium silicate and hydrochloric acid are reacted to produce orthosilicic acid precipitate, and then the orthosilicic acid precipitate is hydrolyzed at high temperature to produce nano silicon dioxide particles, so that silica sol is obtained;
(3) mixing the obtained silica sol and mussel mucin according to the mass ratio of 10:1 to obtain a mixed solution, dripping ammonia water into the mixed solution to adjust the pH value to 8, heating to 35-45 ℃, standing for reaction for 3-5 h, continuously adding catechol oxidase accounting for 5% of the mass of the mixed solution, and continuously standing for reaction for 6-8 h to obtain a plastic wear-resistant reinforcing material; firstly, because 10% of dopa groups exist in mussel mucin peptide chain fragments, under the condition of higher pH value, some phenolic hydroxyl groups in the dopa groups are oxidized into quinones, the process is accelerated in the presence of catechol oxidase, oxidized dopa and unoxidized dopa are crosslinked to form a high-molecular reticular polymer which is attached to the surface of nano silica in silica sol, so that the surface of inorganic silica is polymerized and materialized to serve as a transition layer, the compatibility between the inorganic silica and a plastic polymer is increased, the cohesive force of a plastic-wood tray is further improved, the mechanical strength of the plastic-wood tray is increased, the inorganic property of the nano silica forms a physical nano self-assembly barrier through self-assembly and crosslinking of nano particles, the mechanical property of the whole plastic-wood material can be improved, the mechanical strength is enhanced, and in addition, the ball bearing function of the nano silica self-assembly barrier, the wear-resistant and wear-reducing capacity of the wood-plastic composite material can be improved, internal energy consumption caused by the wear of the wood-plastic composite material is reduced through rolling sliding among particles, the wear-resistant effect of the material is further improved, and the nano silicon dioxide particles can also fill dents on the wear surface, so that the subsequent friction is reduced, and the wear-resistant performance of the wood-plastic composite material is further improved;
(4) mixing a copper sulfate solution with the mass fraction of 30% and coconut oil fatty acid diethanolamide according to the mass ratio of 10:1, putting the mixture into an ultrasonic oscillator, and carrying out ultrasonic oscillation treatment for 15-20 min at the frequency of 30-40 kHz to obtain a microemulsion;
(5) heating the microemulsion to 40-50 ℃, putting the microemulsion into an electrodeposition device, and keeping the current density at 0.05-0.2A/cm2Carrying out electrodeposition treatment for 20-30 min under the condition that the distance between the polar plates is 10-20 mm, carrying out centrifugal separation on the microemulsion subjected to electrodeposition treatment to obtain filter residues, and carrying out vacuum drying to obtain the nano copper powder;
(6) putting the obtained nano copper powder into a hydrochloric acid solution with the mass fraction of 6%, performing dealloying corrosion treatment for 8-11 h to obtain modified nano copper powder after the treatment is finished, mixing the modified nano copper powder and polytetrafluoroethylene according to the mass ratio of 1:10, then putting the mixture into an internal mixer, carrying out internal mixing at 300-320 ℃ for 1-2 h, and then extruding and granulating the mixture through a screw extruder to obtain self-made wear-resistant particles; because the polytetrafluoroethylene is mainly composed of a cylindrical shell which is completely surrounded by fluorine atoms and is composed of a carbon-carbon main chain spiral structure, and the cylindrical structure makes the attraction between polytetrafluoroethylene molecules very weak so as to be easy to slide, when the polytetrafluoroethylene is subjected to external friction stress, the internal wear energy consumption of the material can be weakened through the intermolecular sliding so as to improve the wear resistance of the material, and the addition of the porous nano copper dioxide particles in the polytetrafluoroethylene has the advantages that on one hand, the surface of the porous nano copper structure is rough, the friction coefficient of the material can be increased, the wear resistance of the material is further improved, the pore structure of the rough nano copper powder particles can be used as a physical anchoring point combined with a polymer material, the internal binding force between the porous nano copper dioxide particles and the polymer material is increased, the cohesion and the cohesion of the wood-plastic material are improved, and the mechanical property of the wood-plastic material is effectively improved, the porous copper nanoparticles can also fill the dents on the wear surface, so that the friction is reduced, and the wear resistance of the wood-plastic material is improved again;
(7) weighing 70-80 parts of waste plastics, 10-20 parts of treated sawdust, 10-15 parts of straws, 5-15 parts of plastic wear-resistant reinforcing materials, 8-10 parts of self-made wear-resistant particles, 1-3 parts of auxiliaries and 2-5 parts of lubricants in parts by weight;
(8) putting the waste plastics into a mixing roll for stirring and mixing, stopping when mixing is sufficient, adding the plastic anti-wear reinforcing material and the self-made anti-wear particles, and continuously mixing fully to obtain modified plastics; the waste plastic is any one of a waste film, a plastic bag, a plastic express bag, a plastic bottle and a plastic sheet; the mixing roll adopts a W-shaped cylinder body and a sleeve type device, so that the clearance between the stirring paddle and the cylinder wall is consistent, and the stirring effect is optimal;
(9) putting the modified plastic and the processed sawdust into a mixing roll, mixing for 5-20 min, stirring at a rotating speed of 200-700 r/min, adding an auxiliary agent, and stirring to obtain a prefabricated object; the auxiliary agent is any one of silane coupling agent, titanate coupling agent or aluminate coupling agent;
(10) mixing the prefabricated object with a lubricant, and continuously stirring and heating to 100-300 ℃ to form a fluid mixture; the lubricant is any one of paraffin, stearic acid or stearate;
(11) and adding the mixture into a single-screw extruder, and extruding by using the single-screw extruder to obtain the high-strength wear-resistant wood-plastic composite material. The power of the single-screw extruder is 0.75KW, and a cycloidal pin gear speed reducing motor is used; the tray mould press is 4.0-7.5 KW in power, and the heating mode is steam heating or heat conducting oil heating.
The preparation process of the wood-plastic composite material comprises the following steps:
(1) pretreatment of raw materials: the manufacturing of the wood-plastic composite material is based on the treatment of raw materials, firstly, the sawdust is treated, and the pore structure of the sawdust is widened through repeated freeze thawing treatment, so that the specific surface area of the sawdust is increased, the contact probability of the sawdust and plastic can be increased, the compatibility of the sawdust and the plastic is improved, the cohesion of the wood-plastic composite material is improved, and the mechanical strength of the wood-plastic composite material is improved; secondly, modifying the plastic, namely firstly utilizing sodium silicate and hydrochloric acid to react to produce orthosilicic acid precipitate, and then hydrolyzing the orthosilicic acid precipitate at high temperature to produce nano silicon dioxide particles so as to obtain silica sol; then adding mussel mucin, because 10% of dopa group is in the peptide chain segment of the mussel mucin, under the condition of higher PH value, some phenolic hydroxyl groups in the dopa group are oxidized into quinone, the process is accelerated in the presence of catechol oxidase, the oxidized dopa and unoxidized dopa are crosslinked to form a high-molecular network polymer which is attached to the surface of nano silicon dioxide in silica sol, so that the inorganic silicon dioxide surface is polymerized and used as a transition layer to increase the compatibility between the inorganic silicon dioxide and the plastic polymer, thereby improving the cohesion of the plastic-wood tray, increasing the mechanical strength of the plastic-wood tray, and improving the inorganic property of the nano silicon dioxide, a physical nano self-assembly barrier is formed by self-assembly and crosslinking of nano particles, so that the mechanical property of the whole plastic-wood material is improved, and the mechanical strength is enhanced. The wood-plastic composite product has wide sources of the used waste plastics, so that the resources can be effectively utilized, and the waste plastics can be prevented from polluting the environment;
secondly, the invention also adds the self-made anti-wear particles composed of polytetrafluoroethylene and porous nano copper powder, because the polytetrafluoroethylene is mainly composed of a cylindrical shell which is completely surrounded by fluorine atoms and is composed of a carbon-carbon main chain spiral structure, and the cylindrical structure makes the attraction between polytetrafluoroethylene molecules very weak so as to be easy to slide, when the polytetrafluoroethylene is subjected to external friction stress, the internal wear energy consumption of the material can be weakened through the intermolecular sliding, thereby improving the anti-wear property of the material, and the addition of the porous nano copper dioxide particles in the polytetrafluoroethylene can increase the friction coefficient of the material and further improve the wear resistance of the material on one hand, and the pore structure of the rough nano copper powder particles can be used as a physical anchoring point combined with a polymeric material to increase the internal bonding force between the porous nano copper dioxide particles and the polymeric material, the cohesion of the wood-plastic material is improved, the mechanical property of the wood-plastic material is effectively improved, and the porous copper nanoparticles can also fill the dents on the wear surface, so that the friction is reduced, and the wear resistance of the wood-plastic material is improved again;
(2) raw material mixing and plasticizing
In the manufacturing process of the wood-plastic composite material plate, after wood chip materials and waste plastics are pretreated, the next step is to mix the prepared wood powder and plastic products made of the waste plastics, add a certain amount of auxiliary agents, fully mix the wood powder and plastic crushed materials according to a certain proportion, add the mixture into equipment, heat the materials after fully mixing to melt the lubricant, and uniformly mix the plastic and the wood powder. The key to the good and bad performance of the wood-plastic composite material is that the plastic and the wood dust are manufactured into a formula of mixing the wood powder and the wood dust. In consideration of the requirements of the wood-plastic composite product and the production process thereof, the key factors for mixing and proportioning the wood-plastic composite product and the production process are as follows: the wood-plastic composite material has the advantages of high rigidity of the wood chips, a reinforcing agent for improving the strength of the wood-plastic composite material, a coupling agent for improving the full fusion of the plastic and the wood powder, an oxidant for preventing the wood powder made of the wood chips from being degraded in the processing process, and the like.
(3) Low-speed mixing granulation of mixture of wood powder and plastic
The biological fiber supercritical fluid plasticizing and granulating technology is a unique technology which is used for generating chemical reaction by applying a physical principle according to the requirement of the traditional wood-plastic two-phase interface treatment so as to achieve a better mixing and melting effect of the wood-plastic two phases. It is expressed as follows: without adding any chemical auxiliary agent, only using clean water as main medium (including fiber containing water or adding water externally), less or no resin material is mixed, and the product similar to plastic is plasticized, and the physical and mechanical index of the product is generally not lower than that of the traditional plastic material. Any substance in the nature can complete the transformation of the form under different conditions, such as the transformation of a forest buried underground ancient times into petroleum and coal. This conversion requires high temperature, high pressure, moisture, and time. The supercritical fluid plasticizing technology is just one environment which is artificially created. For example, the instantaneous maximum temperature of the material treatment can reach more than 1000 ℃, and the carbonization critical point of the wood chips also reaches 2800 ℃, which is much higher than the control temperature of the common wood-plastic compound and the product extrusion. The control technology of the critical point of the material form transformation is a key node of the technology.
The granulation technology of the biological fiber supercritical fluid is mainly characterized in that: the addition amount of the wood powder in the wood-plastic mixture ratio can reach more than 80 percent, so that the raw material cost is greatly reduced; no auxiliary agent is added in the wood-plastic granulation, so that the cost is saved and the environmental pollution can be avoided; the wood-plastic particles have high plasticity and good extensibility and are very wide in application field and industry; the granulation equipment is simple in configuration, convenient to operate and convenient to copy, and has the condition of enlarging reproduction; the existing wood-plastic forming machine can be basically used without large-scale equipment updating.
Example 1
(1) And (3) wood chip treatment:
weighing sawdust, soaking in deionized water for 15h, taking out the soaked sawdust, immediately spraying and freezing with liquid nitrogen for 2min, heating to 40 ℃ after spraying, thawing for 10min, and repeatedly freezing and thawing for 5 times to obtain treated sawdust; through repeated freeze thawing treatment, the pore structure of the sawdust is widened, the specific surface area of the sawdust is increased, the contact probability of the sawdust and the plastic can be increased, the compatibility of the sawdust and the plastic is improved, the cohesion of the plastic-wood tray is improved, and the mechanical strength of the plastic-wood tray is increased;
(2) pouring a sodium silicate solution with the concentration of 0.5mol/L into a beaker, regulating the pH to 6.0 by using hydrochloric acid with the concentration of 1mol/L, stirring and reacting for 1h by using a magnetic stirrer at the rotating speed of 300r/min, moving into a reaction kettle after the reaction is finished, heating to 150 ℃, and carrying out heat preservation hydrolysis reaction for 2h to obtain self-made silica sol; firstly, sodium silicate and hydrochloric acid are reacted to produce orthosilicic acid precipitate, and then the orthosilicic acid precipitate is hydrolyzed at high temperature to produce nano silicon dioxide particles, so that silica sol is obtained;
(3) mixing the obtained silica sol and mussel mucin according to the mass ratio of 10:1 to obtain a mixed solution, dripping ammonia water into the mixed solution to adjust the pH value to 8, heating to 35 ℃, standing for reaction for 3 hours, then continuously adding catechol oxidase accounting for 5 percent of the mass of the mixed solution, and continuously standing for reaction for 6 hours to obtain the plastic anti-wear reinforcing material; firstly, because 10% of dopa groups exist in mussel mucin peptide chain fragments, under the condition of higher pH value, some phenolic hydroxyl groups in the dopa groups are oxidized into quinones, the process is accelerated in the presence of catechol oxidase, oxidized dopa and unoxidized dopa are crosslinked to form a high-molecular reticular polymer which is attached to the surface of nano silica in silica sol, so that the surface of inorganic silica is polymerized and materialized to serve as a transition layer, the compatibility between the inorganic silica and a plastic polymer is increased, the cohesive force of a plastic-wood tray is further improved, the mechanical strength of the plastic-wood tray is increased, the inorganic property of the nano silica forms a physical nano self-assembly barrier through self-assembly and crosslinking of nano particles, the mechanical property of the whole plastic-wood material can be improved, the mechanical strength is enhanced, and in addition, the ball bearing function of the nano silica self-assembly barrier, the wear-resistant and wear-reducing capacity of the wood-plastic composite material can be improved, internal energy consumption caused by the wear of the wood-plastic composite material is reduced through rolling sliding among particles, the wear-resistant effect of the material is further improved, and the nano silicon dioxide particles can also fill dents on the wear surface, so that the subsequent friction is reduced, and the wear-resistant performance of the wood-plastic composite material is further improved;
(4) mixing a copper sulfate solution with the mass fraction of 30% and coconut oil fatty acid diethanolamide according to the mass ratio of 10:1, putting the mixture into an ultrasonic oscillator, and carrying out ultrasonic oscillation treatment for 15min at the frequency of 30kHz to obtain a microemulsion;
(5) heating the microemulsion to 40 deg.C, placing into an electrodeposition device, and controlling current density at 0.05A/cm2Carrying out electrodeposition treatment for 20min under the condition that the distance between the polar plates is 10mm, carrying out centrifugal separation on the microemulsion subjected to electrodeposition treatment to obtain filter residue, and carrying out vacuum drying to obtain the nano copper powder;
(6) placing the obtained nano copper powder into a hydrochloric acid solution with the mass fraction of 6%, performing dealloying corrosion treatment for 8 hours to obtain modified nano copper powder after the treatment is finished, mixing the modified nano copper powder and polytetrafluoroethylene according to the mass ratio of 1:10, then placing the mixture into an internal mixer, carrying out internal mixing at 300 ℃ for 1 hour, and then carrying out extrusion granulation by a screw extruder to obtain self-made wear-resistant particles; because the polytetrafluoroethylene is mainly composed of a cylindrical shell which is completely surrounded by fluorine atoms and is composed of a carbon-carbon main chain spiral structure, and the cylindrical structure makes the attraction between polytetrafluoroethylene molecules very weak so as to be easy to slide, when the polytetrafluoroethylene is subjected to external friction stress, the internal wear energy consumption of the material can be weakened through the intermolecular sliding so as to improve the wear resistance of the material, and the addition of the porous nano copper dioxide particles in the polytetrafluoroethylene has the advantages that on one hand, the surface of the porous nano copper structure is rough, the friction coefficient of the material can be increased, the wear resistance of the material is further improved, the pore structure of the rough nano copper powder particles can be used as a physical anchoring point combined with a polymer material, the internal binding force between the porous nano copper dioxide particles and the polymer material is increased, the cohesion and the cohesion of the wood-plastic material are improved, and the mechanical property of the wood-plastic material is effectively improved, the porous copper nanoparticles can also fill the dents on the wear surface, so that the friction is reduced, and the wear resistance of the wood-plastic material is improved again;
(7) weighing 70 parts of waste plastics, 10 parts of treated sawdust, 10 parts of straws, 5 parts of plastic anti-wear reinforcing materials, 8 parts of self-made anti-wear particles, 1 part of auxiliary agents and 2 parts of lubricating agents in parts by weight;
(8) putting the waste film into a mixing roll for stirring and mixing, stopping when mixing is sufficient, adding the plastic anti-wear reinforcing material and the self-made anti-wear particles, and continuously mixing fully to obtain modified plastic;
(9) putting the modified plastic and the processed wood chips into a mixing roll to mix for 5min, stirring at the rotating speed of 200r/min, adding a silane coupling agent, and stirring to obtain a prefabricated object;
(10) mixing the prefabricated object with paraffin, and continuously stirring and heating to 100 ℃ to form a fluid mixture;
(11) and adding the mixture into a single-screw extruder, and extruding by using the single-screw extruder to obtain the high-strength wear-resistant wood-plastic composite material. The power of the single-screw extruder is 0.75KW, and a cycloidal pin gear speed reducing motor is used; the tray molding press is 4.0KW in power, and the heating mode is steam heating or heat conduction oil heating.
Example 2
(1) And (3) wood chip treatment:
weighing sawdust, soaking in deionized water for 16h, taking out the soaked sawdust, immediately spraying and freezing with liquid nitrogen for 3min, heating to 42 ℃ after spraying, thawing for 12min, and repeatedly freezing and thawing for 6 times to obtain treated sawdust; through repeated freeze thawing treatment, the pore structure of the sawdust is widened, the specific surface area of the sawdust is increased, the contact probability of the sawdust and the plastic can be increased, the compatibility of the sawdust and the plastic is improved, the cohesion of the plastic-wood tray is improved, and the mechanical strength of the plastic-wood tray is increased;
(2) pouring 0.5mol/L sodium silicate solution into a beaker, regulating the pH to 6.0 by using 1mol/L hydrochloric acid, stirring and reacting for 1h by using a magnetic stirrer at the rotating speed of 320r/min, moving into a reaction kettle after the reaction is finished, heating to 160 ℃, and carrying out heat preservation hydrolysis reaction for 3h to obtain self-made silica sol; firstly, sodium silicate and hydrochloric acid are reacted to produce orthosilicic acid precipitate, and then the orthosilicic acid precipitate is hydrolyzed at high temperature to produce nano silicon dioxide particles, so that silica sol is obtained;
(3) mixing the obtained silica sol and mussel mucin according to the mass ratio of 10:1 to obtain a mixed solution, dripping ammonia water into the mixed solution to adjust the pH value to 8, heating to 38 ℃, standing for reaction for 4 hours, continuously adding catechol oxidase accounting for 5 percent of the mass of the mixed solution, and continuously standing for reaction for 7 hours to obtain the plastic anti-wear reinforcing material; firstly, because 10% of dopa groups exist in mussel mucin peptide chain fragments, under the condition of higher pH value, some phenolic hydroxyl groups in the dopa groups are oxidized into quinones, the process is accelerated in the presence of catechol oxidase, oxidized dopa and unoxidized dopa are crosslinked to form a high-molecular reticular polymer which is attached to the surface of nano silica in silica sol, so that the surface of inorganic silica is polymerized and materialized to serve as a transition layer, the compatibility between the inorganic silica and a plastic polymer is increased, the cohesive force of a plastic-wood tray is further improved, the mechanical strength of the plastic-wood tray is increased, the inorganic property of the nano silica forms a physical nano self-assembly barrier through self-assembly and crosslinking of nano particles, the mechanical property of the whole plastic-wood material can be improved, the mechanical strength is enhanced, and in addition, the ball bearing function of the nano silica self-assembly barrier, the wear-resistant and wear-reducing capacity of the wood-plastic composite material can be improved, internal energy consumption caused by the wear of the wood-plastic composite material is reduced through rolling sliding among particles, the wear-resistant effect of the material is further improved, and the nano silicon dioxide particles can also fill dents on the wear surface, so that the subsequent friction is reduced, and the wear-resistant performance of the wood-plastic composite material is further improved;
(4) mixing a copper sulfate solution with the mass fraction of 30% and coconut oil fatty acid diethanolamide according to the mass ratio of 10:1, putting the mixture into an ultrasonic oscillator, and carrying out ultrasonic oscillation treatment for 17min at the frequency of 32kHz to obtain a microemulsion;
(5) heating the microemulsion to 42 deg.C, placing into an electrodeposition device, and controlling current density at 0.12A/cm2Carrying out electrodeposition treatment for 23min under the condition that the distance between the polar plates is 13mm, carrying out centrifugal separation on the microemulsion subjected to the electrodeposition treatment to obtain filter residues, and carrying out vacuum drying to obtain the nano copper powder;
(6) placing the obtained nano copper powder into a hydrochloric acid solution with the mass fraction of 6%, performing dealloying corrosion treatment for 9 hours to obtain modified nano copper powder after the treatment is finished, mixing the modified nano copper powder and polytetrafluoroethylene according to the mass ratio of 1:10, then placing the mixture into an internal mixer, carrying out internal mixing at 305 ℃ for 1 hour, and then carrying out extrusion granulation through a screw extruder to obtain self-made wear-resistant particles; because the polytetrafluoroethylene is mainly composed of a cylindrical shell which is completely surrounded by fluorine atoms and is composed of a carbon-carbon main chain spiral structure, and the cylindrical structure makes the attraction between polytetrafluoroethylene molecules very weak so as to be easy to slide, when the polytetrafluoroethylene is subjected to external friction stress, the internal wear energy consumption of the material can be weakened through the intermolecular sliding so as to improve the wear resistance of the material, and the addition of the porous nano copper dioxide particles in the polytetrafluoroethylene has the advantages that on one hand, the surface of the porous nano copper structure is rough, the friction coefficient of the material can be increased, the wear resistance of the material is further improved, the pore structure of the rough nano copper powder particles can be used as a physical anchoring point combined with a polymer material, the internal binding force between the porous nano copper dioxide particles and the polymer material is increased, the cohesion and the cohesion of the wood-plastic material are improved, and the mechanical property of the wood-plastic material is effectively improved, the porous copper nanoparticles can also fill the dents on the wear surface, so that the friction is reduced, and the wear resistance of the wood-plastic material is improved again;
(7) weighing 72 parts of waste plastics, 13 parts of processed sawdust, 11 parts of straws, 7 parts of plastic anti-wear reinforcing materials, 9 parts of self-made anti-wear particles, 2 parts of auxiliaries and 3 parts of lubricants according to parts by weight;
(8) putting the waste plastic bags into a mixing roll for stirring and mixing, stopping when mixing is sufficient, adding plastic anti-wear reinforcing materials and self-made anti-wear particles, and continuously mixing fully to obtain modified plastic;
(9) putting the modified plastic and the processed wood chips into a mixing roll to mix for 9min, stirring at the rotating speed of 300r/min, adding a titanate coupling agent, and stirring to obtain a prefabricated object;
(10) mixing the prefabricated object with stearic acid, and continuously stirring and heating to 140 ℃ to form a fluid mixture;
(11) and adding the mixture into a single-screw extruder, and extruding by using the single-screw extruder to obtain the high-strength wear-resistant wood-plastic composite material. The power of the single-screw extruder is 0.75KW, and a cycloidal pin gear speed reducing motor is used; the tray molding press is 5.2KW in power, and the heating mode is steam heating or heat conducting oil heating.
Example 3
(1) And (3) wood chip treatment:
weighing sawdust, soaking in deionized water for 18h, taking out the soaked sawdust, immediately spraying and freezing with liquid nitrogen for 3min, heating to 46 ℃ after spraying, thawing for 14min, and repeatedly freezing and thawing for 7 times to obtain treated sawdust; through repeated freeze thawing treatment, the pore structure of the sawdust is widened, the specific surface area of the sawdust is increased, the contact probability of the sawdust and the plastic can be increased, the compatibility of the sawdust and the plastic is improved, the cohesion of the plastic-wood tray is improved, and the mechanical strength of the plastic-wood tray is increased;
(2) pouring 0.5mol/L sodium silicate solution into a beaker, regulating the pH to 6.0 by using 1mol/L hydrochloric acid, stirring and reacting for 2 hours by using a magnetic stirrer at a rotating speed of 360r/min, moving into a reaction kettle after the reaction is finished, heating to 180 ℃, and carrying out heat preservation hydrolysis reaction for 3 hours to obtain self-made silica sol; firstly, sodium silicate and hydrochloric acid are reacted to produce orthosilicic acid precipitate, and then the orthosilicic acid precipitate is hydrolyzed at high temperature to produce nano silicon dioxide particles, so that silica sol is obtained;
(3) mixing the obtained silica sol and mussel mucin according to the mass ratio of 10:1 to obtain a mixed solution, dripping ammonia water into the mixed solution to adjust the pH value to 8, heating to 42 ℃, standing for reaction for 4 hours, continuously adding catechol oxidase accounting for 5 percent of the mass of the mixed solution, and continuously standing for reaction for 7 hours to obtain the plastic anti-wear reinforcing material; firstly, because 10% of dopa groups exist in mussel mucin peptide chain fragments, under the condition of higher pH value, some phenolic hydroxyl groups in the dopa groups are oxidized into quinones, the process is accelerated in the presence of catechol oxidase, oxidized dopa and unoxidized dopa are crosslinked to form a high-molecular reticular polymer which is attached to the surface of nano silica in silica sol, so that the surface of inorganic silica is polymerized and materialized to serve as a transition layer, the compatibility between the inorganic silica and a plastic polymer is increased, the cohesive force of a plastic-wood tray is further improved, the mechanical strength of the plastic-wood tray is increased, the inorganic property of the nano silica forms a physical nano self-assembly barrier through self-assembly and crosslinking of nano particles, the mechanical property of the whole plastic-wood material can be improved, the mechanical strength is enhanced, and in addition, the ball bearing function of the nano silica self-assembly barrier, the wear-resistant and wear-reducing capacity of the wood-plastic composite material can be improved, internal energy consumption caused by the wear of the wood-plastic composite material is reduced through rolling sliding among particles, the wear-resistant effect of the material is further improved, and the nano silicon dioxide particles can also fill dents on the wear surface, so that the subsequent friction is reduced, and the wear-resistant performance of the wood-plastic composite material is further improved;
(4) mixing a copper sulfate solution with the mass fraction of 30% and coconut oil fatty acid diethanolamide according to the mass ratio of 10:1, putting the mixture into an ultrasonic oscillator, and carrying out ultrasonic oscillation treatment for 18min at the frequency of 38kHz to obtain a microemulsion;
(5) heating the microemulsion to 48 deg.C, placing into an electrodeposition device, and controlling current density at 0.18A/cm2Performing electrodeposition treatment for 28min under the condition that the distance between the polar plates is 18mm, and performing electrodepositionCentrifuging the treated microemulsion to obtain filter residue, and vacuum drying to obtain nanometer copper powder;
(6) placing the obtained nano copper powder into a hydrochloric acid solution with the mass fraction of 6%, performing dealloying corrosion treatment for 10 hours to obtain modified nano copper powder after the treatment is finished, mixing the modified nano copper powder and polytetrafluoroethylene according to the mass ratio of 1:10, then placing the mixture into an internal mixer, carrying out internal mixing at 315 ℃ for 2 hours, and then carrying out extrusion granulation through a screw extruder to obtain self-made wear-resistant particles; because the polytetrafluoroethylene is mainly composed of a cylindrical shell which is completely surrounded by fluorine atoms and is composed of a carbon-carbon main chain spiral structure, and the cylindrical structure makes the attraction between polytetrafluoroethylene molecules very weak so as to be easy to slide, when the polytetrafluoroethylene is subjected to external friction stress, the internal wear energy consumption of the material can be weakened through the intermolecular sliding so as to improve the wear resistance of the material, and the addition of the porous nano copper dioxide particles in the polytetrafluoroethylene has the advantages that on one hand, the surface of the porous nano copper structure is rough, the friction coefficient of the material can be increased, the wear resistance of the material is further improved, the pore structure of the rough nano copper powder particles can be used as a physical anchoring point combined with a polymer material, the internal binding force between the porous nano copper dioxide particles and the polymer material is increased, the cohesion and the cohesion of the wood-plastic material are improved, and the mechanical property of the wood-plastic material is effectively improved, the porous copper nanoparticles can also fill the dents on the wear surface, so that the friction is reduced, and the wear resistance of the wood-plastic material is improved again;
(7) weighing 78 parts of waste plastic, 18 parts of treated sawdust, 14 parts of straw, 13 parts of plastic anti-wear reinforcing material, 9 parts of self-made anti-wear particles, 3 parts of auxiliary agent and 4 parts of lubricating agent according to parts by weight;
(8) putting the waste plastic express bag into a mixing roll for stirring and mixing, stopping when mixing is sufficient, adding the plastic anti-wear reinforcing material and the self-made anti-wear particles, and continuously mixing fully to obtain modified plastic;
(9) putting the modified plastic and the processed wood chips into a mixing roll to mix for 18min, stirring at the rotating speed of 600r/min, adding an aluminate coupling agent, and stirring to obtain a prefabricated object;
(10) mixing the prefabricated material with sodium stearate, and continuously stirring and heating to 280 ℃ to form a fluid mixture;
(11) and adding the mixture into a single-screw extruder, and extruding by using the single-screw extruder to obtain the high-strength wear-resistant wood-plastic composite material. The power of the single-screw extruder is 0.75KW, and a cycloidal pin gear speed reducing motor is used; the tray molding press is 7.2KW in power, and the heating mode is steam heating or heat conducting oil heating.
Example 4
(1) And (3) wood chip treatment:
weighing sawdust, soaking in deionized water for 20h, taking out the soaked sawdust, immediately spraying and freezing with liquid nitrogen for 3min, heating to 50 ℃ after spraying, thawing for 15min, and repeatedly freezing and thawing for 8 times to obtain treated sawdust; through repeated freeze thawing treatment, the pore structure of the sawdust is widened, the specific surface area of the sawdust is increased, the contact probability of the sawdust and the plastic can be increased, the compatibility of the sawdust and the plastic is improved, the cohesion of the plastic-wood tray is improved, and the mechanical strength of the plastic-wood tray is increased;
(2) pouring a sodium silicate solution with the concentration of 0.5mol/L into a beaker, regulating the pH to 6.0 by using hydrochloric acid with the concentration of 1mol/L, stirring and reacting for 2 hours by using a magnetic stirrer at the rotating speed of 400r/min, moving into a reaction kettle after the reaction is finished, heating to 200 ℃, and carrying out thermal insulation hydrolysis reaction for 3 hours to obtain self-made silica sol; firstly, sodium silicate and hydrochloric acid are reacted to produce orthosilicic acid precipitate, and then the orthosilicic acid precipitate is hydrolyzed at high temperature to produce nano silicon dioxide particles, so that silica sol is obtained;
(3) mixing the obtained silica sol and mussel mucin according to the mass ratio of 10:1 to obtain a mixed solution, dripping ammonia water into the mixed solution to adjust the pH value to 8, heating to 45 ℃, standing for 5 hours for reaction, continuously adding catechol oxidase accounting for 5 percent of the mass of the mixed solution, and continuously standing for reaction for 8 hours to obtain the plastic anti-wear reinforcing material; firstly, because 10% of dopa groups exist in mussel mucin peptide chain fragments, under the condition of higher pH value, some phenolic hydroxyl groups in the dopa groups are oxidized into quinones, the process is accelerated in the presence of catechol oxidase, oxidized dopa and unoxidized dopa are crosslinked to form a high-molecular reticular polymer which is attached to the surface of nano silica in silica sol, so that the surface of inorganic silica is polymerized and materialized to serve as a transition layer, the compatibility between the inorganic silica and a plastic polymer is increased, the cohesive force of a plastic-wood tray is further improved, the mechanical strength of the plastic-wood tray is increased, the inorganic property of the nano silica forms a physical nano self-assembly barrier through self-assembly and crosslinking of nano particles, the mechanical property of the whole plastic-wood material can be improved, the mechanical strength is enhanced, and in addition, the ball bearing function of the nano silica self-assembly barrier, the wear-resistant and wear-reducing capacity of the wood-plastic composite material can be improved, internal energy consumption caused by the wear of the wood-plastic composite material is reduced through rolling sliding among particles, the wear-resistant effect of the material is further improved, and the nano silicon dioxide particles can also fill dents on the wear surface, so that the subsequent friction is reduced, and the wear-resistant performance of the wood-plastic composite material is further improved;
(4) mixing a copper sulfate solution with the mass fraction of 30% and coconut oil fatty acid diethanolamide according to the mass ratio of 10:1, putting the mixture into an ultrasonic oscillator, and carrying out ultrasonic oscillation treatment for 20min at the frequency of 40kHz to obtain a microemulsion;
(5) heating the microemulsion to 50 deg.C, placing into an electrodeposition device, and controlling current density at 0.2A/cm2Carrying out electrodeposition treatment for 30min under the condition that the distance between the polar plates is 20mm, carrying out centrifugal separation on the microemulsion subjected to electrodeposition treatment to obtain filter residue, and carrying out vacuum drying to obtain the nano copper powder;
(6) placing the obtained nano copper powder into a hydrochloric acid solution with the mass fraction of 6%, performing dealloying corrosion treatment for 11h to obtain modified nano copper powder after the treatment is finished, mixing the modified nano copper powder and polytetrafluoroethylene according to the mass ratio of 1:10, then placing the mixture into an internal mixer, banburying the mixture at 320 ℃ for 2h, and then extruding and granulating the mixture through a screw extruder to obtain self-made wear-resistant particles; because the polytetrafluoroethylene is mainly composed of a cylindrical shell which is completely surrounded by fluorine atoms and is composed of a carbon-carbon main chain spiral structure, and the cylindrical structure makes the attraction between polytetrafluoroethylene molecules very weak so as to be easy to slide, when the polytetrafluoroethylene is subjected to external friction stress, the internal wear energy consumption of the material can be weakened through the intermolecular sliding so as to improve the wear resistance of the material, and the addition of the porous nano copper dioxide particles in the polytetrafluoroethylene has the advantages that on one hand, the surface of the porous nano copper structure is rough, the friction coefficient of the material can be increased, the wear resistance of the material is further improved, the pore structure of the rough nano copper powder particles can be used as a physical anchoring point combined with a polymer material, the internal binding force between the porous nano copper dioxide particles and the polymer material is increased, the cohesion and the cohesion of the wood-plastic material are improved, and the mechanical property of the wood-plastic material is effectively improved, the porous copper nanoparticles can also fill the dents on the wear surface, so that the friction is reduced, and the wear resistance of the wood-plastic material is improved again;
(7) weighing 80 parts of waste plastics, 20 parts of treated sawdust, 15 parts of straws, 15 parts of plastic anti-wear reinforcing materials, 10 parts of self-made anti-wear particles, 3 parts of auxiliaries and 5 parts of lubricants according to parts by weight;
(8) putting the waste plastic bottles into a mixing roll for stirring and mixing, stopping when mixing is sufficient, adding plastic anti-wear reinforcing materials and self-made anti-wear particles, and continuously mixing fully to obtain modified plastic;
(9) putting the modified plastic and the processed wood chips into a mixing roll to mix for 20min, stirring at the rotating speed of 700r/min, adding an aluminate coupling agent, and stirring to obtain a prefabricated object;
(10) mixing the prefabricated object with stearic acid, and continuously stirring and heating to 300 ℃ to form a fluid mixture;
(11) and adding the mixture into a single-screw extruder, and extruding by using the single-screw extruder to obtain the high-strength wear-resistant wood-plastic composite material. The power of the single-screw extruder is 0.75KW, and a cycloidal pin gear speed reducing motor is used; the tray molding press is 7.5KW in power, and the heating mode is steam heating or heat-conducting oil heating.
Example 5: the preparation process was carried out without adding the treated wood chips of the present invention, and the other conditions and component ratios were the same as in example 1.
Example 6: the home-made anti-wear particles of the present invention were not added during the preparation process, and other conditions and component ratios were the same as in example 1.
Example 7: the plastic reinforced abrasive resistance material of the invention is not added in the preparation process, and other conditions and component ratios are the same as in example 1.
Performance test
The performance tests were performed on examples 1-7, respectively, and the test results are shown in table 1:
detection method/test method
1. And (3) pressure detection: testing by adopting the experimental standard of GB/T4857.4-2008, wherein the experimental temperature is 30 ℃, the humidity is 80%, putting an experimental sample on a pressure testing machine, pressing down at a constant speed of 10mm/min, and recording the maximum pressure value when the deformation of the pressed sample reaches 15 mm;
2. drop test: testing by adopting the experimental standard of GB/T4857.4-1992, wherein the experimental temperature is 30 ℃, the humidity is 80%, the drop height is 1000mm, the experimental sample is hoisted along the diagonal direction and then dropped on an impact surface, the same angle is dropped for 3 times on the same height, and whether appearance change exists or not is observed;
3. abrasion resistance: testing according to a 4.44 part surface wear resistance test-method 3 in the GB17657-2013 standard;
TABLE 1 Performance test results
Figure 648386DEST_PATH_IMAGE001
The performances of examples 1-4 are compared, wherein the mechanical property and the wear resistance in example 4 are optimal, because the proportion of the added materials in example 4 is the highest, the technical scheme of the application is reflected from the side surface to be practicable.
Comparing the performances of the example 1 and the example 4, because no sawdust is added, the mechanical property and the wear resistance of the final material are both obviously reduced, so that the high-strength wear-resistant wood-plastic composite material disclosed by the invention can be used for widening the pore structure of the sawdust through repeated freeze thawing treatment, further increasing the specific surface area of the sawdust, increasing the contact probability of the sawdust and the plastic, improving the compatibility of the sawdust and the plastic, further improving the cohesion of the plastic-wood pallet and increasing the mechanical strength of the plastic-wood pallet;
comparing the performances of the example 1 and the example 5, wherein the example 5 has no self-made anti-wear particles added, so that the mechanical property and the anti-wear property of the final material are both obviously reduced, therefore, the polytetrafluoroethylene mainly comprises a cylindrical shell which is completely surrounded by fluorine atoms and consists of a carbon-carbon main chain spiral structure, and the attraction force among polytetrafluoroethylene molecules is very weak due to the cylindrical structure so as to be easy to slide, so that when the external friction stress is applied, the internal wear energy consumption in the material can be reduced through the intermolecular sliding, so that the anti-wear property of the material is improved, and the addition of the porous nano copper dioxide particles in the polytetrafluoroethylene has the advantages that the surface of the porous nano copper structure is rough, the friction coefficient of the material can be increased, the wear resistance of the material is further improved, and the pore structure of the rough nano copper powder particles can be used as a physical anchoring point combined with a polymeric material, the internal binding force between the porous copper nano particles and the wear-resistant surface is increased, so that the cohesion of the wood-plastic material is improved, the mechanical property of the wood-plastic material is effectively improved, and the porous copper nano particles can also fill the dents on the wear surface, so that the friction is reduced, and the wear resistance of the wood-plastic material is improved again;
comparing the performances of example 1 and example 6, wherein in example 6, no plastic reinforced anti-abrasive material is added, so that the mechanical property and the anti-wear property of the final material are significantly reduced, and thus, by using 10% of dopa groups in mussel mucin peptide chain fragments, some phenolic hydroxyl groups in the dopa groups are oxidized into quinones under the condition of high pH value, the process is accelerated in the presence of catechol oxidase, oxidized dopa and unoxidized dopa are crosslinked to form a macromolecular reticular polymer attached to the surface of nano silica in silica sol, so that the surface of the inorganic silica is polymerized to serve as a transition layer, the compatibility between the inorganic silica and the plastic polymer is increased, the cohesion of the plastic-wood pallet is improved, the mechanical strength of the plastic-wood pallet is increased, and the inorganic property of the nano silica forms a physical nano self-assembly barrier through the self-assembly and crosslinking of nano particles, the mechanical property of the whole plastic-wood material can be improved, the mechanical strength is enhanced, in addition, the ball bearing effect of the nano silicon dioxide self-assembly barrier can improve the wear-resistant and wear-reducing capacity of the wood-plastic composite material, the internal energy consumption generated by the wood-plastic composite material due to wear is reduced through the rolling sliding among particles, the wear-resistant effect of the material is further improved, and the nano silicon dioxide particles can also fill the dents on the wear surface, so that the subsequent friction is reduced, and the wear-resistant performance of the wood-plastic composite material is further improved.
Comparative example
Comparative example 1: the preparation method is basically the same as that of example 1 of the present invention, except that common wood chips are used instead of the treated wood chips of the present invention, and other conditions and component ratios are the same as those in example 1;
comparative example 2: the preparation method is basically the same as that of example 1 of the present invention, except that the home-made anti-wear particles of the present invention are replaced with ordinary copper oxide particles, and the other conditions and component ratios are the same as those in example 1;
comparative example 3: the preparation method is basically the same as that of the example 1 of the invention, except that the common nano-silica is used to replace the plastic reinforced abrasive resistant material of the invention, and other conditions and component proportions are the same as those in the example 1;
performance test
The performance of comparative examples 1 to 3 of the present invention was measured, and the results are shown in table 2:
detection method/test method
1. And (3) pressure detection: testing by adopting the experimental standard of GB/T4857.4-2008, wherein the experimental temperature is 30 ℃, the humidity is 80%, putting an experimental sample on a pressure testing machine, pressing down at a constant speed of 10mm/min, and recording the maximum pressure value when the deformation of the pressed sample reaches 15 mm;
2. drop test: testing by adopting the experimental standard of GB/T4857.4-1992, wherein the experimental temperature is 30 ℃, the humidity is 80%, the drop height is 1000mm, the experimental sample is hoisted along the diagonal direction and then dropped on an impact surface, the same angle is dropped for 3 times on the same height, and whether appearance change exists or not is observed;
3. abrasion resistance: testing according to a 4.44 part surface wear resistance test-method 3 in the GB17657-2013 standard;
TABLE 2 Performance test results
Figure 625700DEST_PATH_IMAGE002
Comparing the performances of the comparative example 1 with those of the example 1 and the example 5, wherein the mechanical property and the wear resistance of the comparative example 1 are obviously reduced compared with those of the example 1, but are superior to those of the example 5, so that the synergistic performance of the treated wood chips on the material is obviously better than that of the untreated wood chips, which also proves that the wood chips treated by the invention have beneficial effects from the side, and the technical scheme can be implemented;
comparing the performances of the comparative example 2 with those of the example 1 and the example 6, wherein the mechanical property and the abrasion resistance of the comparative example 2 are obviously reduced compared with those of the example 1, but are superior to those of the example 6, so that the synergistic performance of the modified copper oxide particles on the material is obviously better than that of the unmodified copper oxide particles, which also proves that the treatment of the copper oxide particles of the invention produces beneficial effects from the side, and the technical scheme can be implemented;
comparing the performances of the comparative example 3 with those of the example 1 and the example 7, wherein the mechanical property and the abrasion resistance of the comparative example 2 are obviously lower than those of the example 1 but better than those of the example 7, so that the synergistic performance of the modified nano silica particles on the material is obviously better than that of the unmodified nano silica particles, which also proves that the treatment of the nano silica particles of the invention produces beneficial effects from the side, and the technical scheme can be implemented;
the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The high-strength wear-resistant wood-plastic composite material is characterized by comprising the following raw materials in parts by weight:
70-80 parts of waste plastic;
treating 10-20 parts of sawdust;
10-15 parts of straw;
1-3 parts of an auxiliary agent;
2-5 parts of a lubricant;
the processed sawdust is prepared by immersing sawdust in water and freezing with liquid nitrogen.
2. The high-strength wear-resistant wood-plastic composite material as claimed in claim 1, further comprising 8-10 parts by weight of self-made wear-resistant particles;
the self-made anti-wear particles are prepared by the reaction of copper sulfate solution, coconut oil fatty acid diethanolamide, hydrochloric acid solution and polytetrafluoroethylene.
3. The high-strength wear-resistant wood-plastic composite material as claimed in claim 1, further comprising 5-15 parts by weight of a plastic wear-resistant reinforcement;
the plastic anti-wear reinforcing material is prepared by reacting sodium silicate solution, hydrochloric acid, mussel mucin and catechol oxidase.
4. A preparation method of a high-strength wear-resistant wood-plastic composite material is characterized by comprising the following specific preparation steps:
(1) weighing 70-80 parts of waste plastics, 10-20 parts of treated sawdust, 10-15 parts of straws, 5-15 parts of plastic wear-resistant reinforcing materials, 8-10 parts of self-made wear-resistant particles, 1-3 parts of auxiliaries and 2-5 parts of lubricants in parts by weight;
(2) putting the waste plastics into a mixing roll for stirring and mixing, stopping when mixing is sufficient, adding the plastic anti-wear reinforcing material and the self-made anti-wear particles, and continuously mixing fully to obtain modified plastics;
(3) putting the modified plastic and the processed sawdust into a mixing roll, mixing for 5-20 min, stirring at a rotating speed of 200-700 r/min, adding an auxiliary agent, and stirring to obtain a prefabricated product, wherein the mixing roll adopts a W-shaped cylinder body and is provided with a sleeve-shaped device, so that the gap between a stirring paddle and the cylinder wall is consistent, and the stirring effect is optimal;
(4) mixing the prefabricated object with a lubricant, and continuously stirring and heating to 100-300 ℃ to form a fluid mixture;
(5) and adding the mixture into a single-screw extruder, and extruding by using the single-screw extruder to obtain the high-strength wear-resistant wood-plastic composite material.
5. The preparation method of the high-strength wear-resistant wood-plastic composite material according to claim 4, wherein the wood chips are treated by the following steps:
weighing sawdust, soaking the sawdust in deionized water for 15-20 h, taking out the soaked sawdust, immediately spraying and freezing the sawdust with liquid nitrogen for 2-3 min, heating to 40-50 ℃ after spraying, thawing for 10-15 min, and repeatedly freezing and thawing for 5-8 times to obtain the treated sawdust.
6. The preparation method of the high-strength anti-wear wood-plastic composite material according to claim 4, wherein the self-made anti-wear particles are prepared by the following steps:
(1) mixing a copper sulfate solution with the mass fraction of 30% and coconut oil fatty acid diethanolamide according to the mass ratio of 10:1, putting the mixture into an ultrasonic oscillator, and carrying out ultrasonic oscillation treatment for 15-20 min at the frequency of 30-40 kHz to obtain a microemulsion;
(2) heating the microemulsion to 40-50 ℃, putting the microemulsion into an electrodeposition device, and keeping the current density at 0.05-0.2A/cm2Carrying out electrodeposition treatment for 20-30 min under the condition that the distance between the polar plates is 10-20 mm, carrying out centrifugal separation on the microemulsion subjected to electrodeposition treatment to obtain filter residues, and carrying out vacuum drying to obtain the nano copper powder;
(3) putting the obtained nano copper powder into a hydrochloric acid solution with the mass fraction of 6%, performing dealloying corrosion treatment for 8-11 h to obtain modified nano copper powder after the treatment is finished, mixing the modified nano copper powder and polytetrafluoroethylene according to the mass ratio of 1:10, putting the mixture into an internal mixer, internally mixing the mixture at 300-320 ℃ for 1-2 h, and extruding and granulating the mixture through a screw extruder to obtain the self-made wear-resistant particles.
7. The preparation method of the high-strength wear-resistant wood-plastic composite material according to claim 4, wherein the preparation steps of the plastic wear-resistant reinforcement are as follows:
(1) weighing sawdust, soaking the sawdust in deionized water for 15-20 h, taking out the soaked sawdust, immediately spraying and freezing the sawdust with liquid nitrogen for 2-3 min, heating to 40-50 ℃ after spraying, thawing for 10-15 min, and repeatedly freezing and thawing for 5-8 times to obtain treated sawdust;
(2) pouring a sodium silicate solution with the concentration of 0.5mol/L into a beaker, adjusting the pH to 6.0 by using hydrochloric acid with the concentration of 1mol/L, stirring and reacting for 1-2 h by using a magnetic stirrer at the rotating speed of 300-400 r/min, moving into a reaction kettle after the reaction is finished, heating to the temperature of 150-200 ℃, and carrying out thermal insulation hydrolysis reaction for 2-3 h to obtain self-prepared silica sol;
(3) mixing the obtained silica sol and mussel mucin according to the mass ratio of 10:1 to obtain a mixed solution, dripping ammonia water into the mixed solution to adjust the pH value to 8, heating to 35-45 ℃, standing for reaction for 3-5 h, then continuously adding catechol oxidase accounting for 5% of the mass of the mixed solution, and continuously standing for reaction for 6-8 h to obtain the plastic anti-wear reinforcing material.
8. The preparation method of the high-strength wear-resistant wood-plastic composite material according to claim 4, wherein the waste plastic in the step (2) is any one of a waste film, a plastic bag, a plastic express bag, a plastic bottle and a plastic sheet.
9. The preparation method of the high-strength wear-resistant wood-plastic composite material as claimed in claim 4, wherein the assistant in the step (3) is any one of a silane coupling agent, a titanate coupling agent or an aluminate coupling agent.
10. The preparation method of the high-strength wear-resistant wood-plastic composite material according to claim 4, wherein the power of the single-screw extruder in the step (5) is 0.75KW, and a cycloidal pin gear speed reduction motor is used.
CN202110037031.4A 2021-01-12 2021-01-12 High-strength wear-resistant wood-plastic composite material and preparation method thereof Pending CN112852181A (en)

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Application publication date: 20210528