CN115322545B - Decrosslinking waste latex reinforced and toughened polylactic acid composite material and preparation method thereof - Google Patents
Decrosslinking waste latex reinforced and toughened polylactic acid composite material and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention discloses a preparation method of a cross-linked waste latex reinforced and toughened polylactic acid composite material, which comprises the following steps: adding expandable graphite and a stripping agent into water, putting into a liquid-phase circulating high-speed shearing and grinding device for shearing, grinding and dispersing, and uniformly dispersing the stripping agent to obtain a dispersion liquid of the stripping agent coated expandable graphite; placing the graphene dispersion liquid into a microwave reaction kettle, and performing microwave irradiation and ultrasonic oscillation synergistic auxiliary expansion reaction to obtain fully-stripped and uniformly-dispersed graphene dispersion liquid; adding the waste latex into graphene dispersion liquid, and placing the graphene dispersion liquid into a microwave reaction kettle to carry out a crosslinking reaction of the latex; and (3) drying the uncrosslinked latex, mixing with polylactic acid, and placing into a melt blending device for melt blending to obtain the high-strength and high-toughness polylactic acid composite material. The invention can efficiently and controllably realize the crosslinking reaction of the waste latex, thereby improving the melt processing performance of the waste latex and obviously improving the comprehensive properties of the polylactic acid composite material such as strength, toughness, conductivity and the like.
Description
Technical Field
The invention relates to a reinforced and toughened polylactic acid composite material obtained by realizing efficient crosslinking of waste latex through microwave-assisted reaction and a preparation method thereof, belonging to the technical field of solid waste resource utilization and polylactic acid high performance.
Background
With the application of latex products in domestic daily use, industry, medical treatment and other industries, a large amount of waste latex is abandoned in landfill every year, and is easy to be a favorable place for breeding of diseases (such as aedes aegypti, dengue fever, chikungunya fever, zika virus and yellow fever) due to the nondegradability of the latex products. The underground water source can be polluted by harmful leachable liquor components, so that the environment is seriously polluted, and the huge waste of resources is caused.
The natural latex in the latex pillow is liquid flowing out when rubber tree cuts rubber, is milky white, has the solid content of 30% -40%, and has the average particle size of about 1.06 mu m. Fresh natural latex contains 27% -41.3% of rubber components and 44% -70% of water, and ammonia and other stabilizers are often added to prevent the natural latex from being coagulated due to the action of microorganisms and enzymes. Zinc diethyldithiocarbamate, benzothiazole accelerator, sulfur-containing vulcanizing machine, silicate and zinc oxide are also required to be added in the foaming process.
In the forming process of the latex pillow, the crosslinking structure formed in the vulcanization process makes recycling and reutilization difficult, and in order to enable the latex pillow to have higher added value, the original three-dimensional crosslinking structure of the latex pillow needs to be destroyed, so that the fluidity of the latex pillow needs to be recovered. Some of the methods currently in common use are: thermomechanical, thermochemical, mechanochemical, biochemical and physical (microwave and ultrasonic) processes. Microwave heating is a high-efficiency and novel material treatment technology, and has wide application in the fields of material science, food processing, analytical chemistry and the like. Since microwaves are electromagnetic waves, they propagate through materials, and the concomitant transmission process results in the dissipation of heat from the electrical energy. However, the microwave energy absorbed by the sample depends on its dielectric properties, the greater the dielectric constant and dielectric dissipation factor, the more microwave power the sample absorbs, and the faster the heating. The advantage of using microwave induced carbonization to recover carbon or solid residues from waste is therefore: compared with the high temperature of 700-900 ℃ in the carbonization process of the waste, the carbonization (or pyrolysis) effect can be realized at a relatively moderate temperature of 400-600 ℃. In the traditional heating method, a heat source is positioned outside carbon, heat generated by the heat source is transmitted through a conduction and radiation mechanism, the surface is heated first and then transferred to the inside, and microwave heating provides volume heating for the inside and the outside of an object at the same time with extremely high efficiency, meanwhile, chemicals are not involved in the heating process, and the method is an environment-friendly and efficient technology.
In order to solve the global problem that the waste latex is not degradable and pollutes the environment, development of a microwave-assisted environment-friendly treatment method is urgently needed to carry out efficient crosslinking reaction on the waste latex, so that the melt processability of the latex is improved, and the method is effectively applied to thermoplastic composite materials.
Disclosure of Invention
The invention aims to overcome the defects of undegradable waste latex and environmental pollution in the prior art, provides an environment-friendly synthesis method capable of efficiently de-crosslinking the waste latex, improves the melt processability of the waste latex, and expands the application of the waste latex in reinforcing and toughening polylactic acid composite materials.
In order to solve the technical problems, the preparation method of the uncrosslinked waste latex reinforced and toughened polylactic acid composite material provided by the invention comprises the following steps:
s1, preparing an intercalation expandable graphite solution: adding the expandable graphite and the stripping agent into water, stirring uniformly, and then placing the mixture into a liquid-phase circulating high-speed shearing and grinding device for shearing, grinding and dispersing, so that the stripping agent is uniformly distributed on the surface of the graphite sheet and between the sheets, and a dispersion liquid of the stripping agent uniformly coating the expandable graphite is obtained;
s2, preparing graphene dispersion liquid: placing the dispersion liquid obtained in the step S1 into a microwave reaction kettle, heating to 200-260 ℃ under built-in ultrasonic vibration, reacting for 2-10 minutes, fully expanding graphite sheets, and stripping the graphite sheets into graphene nano sheets to obtain a dispersion liquid containing uniformly dispersed graphene;
s3, preparing a decrosslinked emulsion: placing the waste latex into the graphene dispersion liquid obtained in the step S2, placing the graphene dispersion liquid into a microwave reaction kettle, heating to 150-220 ℃ under a stirring state, and reacting for 30 seconds-20 minutes to obtain the uncrosslinked latex;
s4, preparing a polylactic acid composite material: and (3) drying the uncrosslinked latex obtained in the step (S3) until the moisture is lower than 0.1%, uniformly mixing the uncrosslinked latex with polylactic acid, and placing the mixture into a melt blending device for melt blending to obtain the polylactic acid composite material.
As an improvement, the fixed carbon content of the expandable graphite in the step S1 is 90% -99.9%, and the size of the graphite flake is 5μm~1500 μm, the mass fraction of the m in the aqueous solution is 0.5% -5%.
As an improvement, the stripping agent in the step S1 is at least one of polyvinylpyrrolidone, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl sulfonate, polyoxyethylene octyl phenol ether-10 and octyl phenol polyoxyethylene ether, and the mass fraction of the stripping agent is 1/200-1/50 of that of the expandable graphite.
As an improvement, the liquid-phase circulation high-speed shearing and grinding equipment for providing the grinding and dispersing function in the step S1 is at least one of a shearing homogenizing emulsifying machine, a pipeline shearing homogenizing emulsifying machine, a vacuum homogenizing emulsifying machine, a rod pin type sand mill and a turbine type sand mill, and the unit mass energy consumption in the grinding and dispersing process is 0.5-10 kWh/kg.
As an improvement, the output power of the microwave reaction kettle in the step S2 is 200-5000W, and the energy consumption per unit mass of the built-in ultrasonic vibration is 1-20 kWh/kg.
As an improvement, the output power of the microwave reaction kettle in the step S3 is 200-5000W, and the mass ratio of graphene to latex is 1/1000-1/50.
As an improvement, the melt blending equipment in the step S4 is at least one of a high-speed mixer, an open mill, a turnover internal mixer, a continuous internal mixer, a reciprocating screw extruder, a double screw extruder, a single screw extruder, a Z-type kneader, a screw kneader, a vacuum kneader and a horizontal double screw mixer, the processing temperature is 80-265 ℃, and the energy consumption per unit mass in the melt blending process is 0.1-5 kWh/kg; the mass ratio of the uncrosslinked latex to the polylactic acid is 1:19-1:1.
The invention also provides the uncrosslinked waste latex reinforced and toughened polylactic acid composite material prepared by the method, and the composite material has good antistatic property, and consists of polylactic acid, uncrosslinked latex and graphene, and has the tensile strength of 50-70 MPa and the impact toughness of 8-30 kJ/m 2 The surface resistance was 1.0X10 8 ~9.9×10 12 Omega, volume resistivity of 1.0X10 7 ~9.9×10 11 Ω·m。
The invention has the beneficial effects that: (1) The liquid-phase circulation high-speed shearing and grinding technology can effectively grind the expandable graphite sheet, and ensures the uniform dispersion and coating of the stripping agent on the surface of the graphite sheet; (2) The technology of combining microwave irradiation and ultrasonic oscillation is adopted to force the graphite sheet to expand in high power, and simultaneously, a good stripping effect is formed; (3) Adding the waste latex into the dispersion liquid of the nano-sheets for uniformly dispersing the graphene, so that the graphene is uniformly adhered inside the latex, the dielectric property of the latex is effectively improved, and the absorption efficiency of microwave irradiation is improved; (4) The high-shear rate melt blending process uniformly disperses the uncrosslinked latex in the polylactic acid matrix and endows good processability, and meanwhile, the graphene nano sheets are fully peeled off to improve the conductivity of the composite material; (5) The composite material has the characteristics of high strength, high toughness, static resistance and the like, and the preparation method has the characteristics of environmental protection, low cost and the like, and is beneficial to expanding the application and development of the uncrosslinked waste latex in the field of multifunctional composite materials. The method adopts a simple and convenient production process, is easy for large-scale and low-cost production, and has multifunction of composite material products.
Drawings
FIG. 1 is a flow chart of a method for preparing a uncrosslinked waste latex reinforced and toughened polylactic acid composite material;
FIG. 2 is a digital photograph of samples of the waste latex (a), the uncrosslinked latex (b) and the high-strength and high-toughness polylactic acid composite (c) in example 1;
FIG. 3 is a scanning electron microscope image of the uncrosslinked latex-reinforced toughened polylactic acid composite material of example 1;
fig. 4 is a scanning electron microscope image of the latex-filled polylactic acid composite material of comparative example 1.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
Example 1
The invention provides a preparation method of a cross-linked waste latex reinforced and toughened polylactic acid composite material, which comprises the following steps:
s11, preparing an intercalation expandable graphite solution: adding 0.5 part by mass of expandable graphite and 0.01 part by mass of stripping agent (sodium dodecyl benzene sulfonate) into 100 parts by mass of water, uniformly stirring, shearing, grinding and dispersing by a vacuum homogenizing emulsifying machine, and obtaining a dispersion liquid of the stripping agent uniformly coating the expandable graphite after the energy consumption per unit mass reaches 0.5 kWh/kg;
s12, preparing graphene dispersion liquid: putting the dispersion liquid obtained in the step S11 into a microwave reaction kettle (with the output power of 200W), heating to 200 ℃, reacting for 10 minutes, enabling the energy consumption per unit mass of built-in ultrasonic vibration to reach 1 kWh/kg, fully expanding and stripping the graphite sheets into graphene nano sheets, and obtaining a dispersion liquid containing uniformly dispersed graphene;
s13, preparing a decrosslinked emulsion: placing 500 parts by mass of waste latex into the graphene dispersion liquid obtained in the step S12, placing into a microwave reaction kettle (output power is 200W), heating to 150 ℃ under a stirring state, and reacting for 20 minutes to obtain the decrosslinked latex;
s14, preparing a polylactic acid composite material: and (3) drying the uncrosslinked latex obtained in the step (S13) until the moisture is lower than 0.1%, uniformly mixing the uncrosslinked latex with 500 parts by mass of polylactic acid, and putting the mixture into a reciprocating screw extruder for melt blending (the processing temperature is 120-195 ℃), so that the high-strength and high-toughness polylactic acid composite material is obtained after the energy consumption per unit mass reaches 0.1 kWh/kg.
Example 2
The invention provides a preparation method of a cross-linked waste latex reinforced and toughened polylactic acid composite material, which comprises the following steps:
s21, preparing an intercalation expandable graphite solution: adding 5 parts by mass of expandable graphite and 0.025 part by mass of stripping agent (polyoxyethylene octyl phenol ether-10) into 100 parts by mass of water, uniformly stirring, shearing, grinding and dispersing by a pin-rod sand mill, and obtaining a dispersion liquid of the stripping agent uniformly coating the expandable graphite after the energy consumption per unit mass reaches 10 kWh/kg;
s22, preparing graphene dispersion liquid: placing the dispersion liquid obtained in the step S21 into a microwave reaction kettle (with the output power of 5000W), heating to 260 ℃, reacting for 2 minutes, enabling the energy consumption per unit mass of built-in ultrasonic vibration to reach 20 kWh/kg, fully expanding and stripping the graphite sheets into graphene nano sheets, and obtaining a dispersion liquid containing uniformly dispersed graphene;
s23, preparing a decrosslinked emulsion: 250 parts by mass of waste latex is placed into graphene dispersion liquid obtained in the step S22, placed into a microwave reaction kettle (output power is 5000W), and heated to 220 ℃ under a stirring state to react for 30 seconds to obtain decrosslinked latex;
s24, preparing a polylactic acid composite material: and (3) drying the uncrosslinked latex obtained in the step (S23) until the moisture is lower than 0.1%, uniformly mixing the uncrosslinked latex with 250 parts by mass of polylactic acid, putting the uncrosslinked latex into a turnover internal mixer for melt blending (the processing temperature is 240-265 ℃), and obtaining the high-strength and high-toughness polylactic acid composite material after the energy consumption per unit mass reaches 5 kWh/kg.
Example 3
The invention provides a preparation method of a cross-linked waste latex reinforced and toughened polylactic acid composite material, which comprises the following steps:
s31, preparing an intercalation expandable graphite solution: adding 1 part by mass of expandable graphite and 0.01 part by mass of stripping agent (polyvinylpyrrolidone) into 100 parts by mass of water, uniformly stirring, shearing, grinding and dispersing by a turbine sand mill, and obtaining a dispersion liquid of the stripping agent uniformly coating the expandable graphite after the energy consumption per unit mass reaches 2 kWh/kg;
s32, preparing graphene dispersion liquid: placing the dispersion liquid obtained in the step S31 into a microwave reaction kettle (with the output power of 1000W), heating to 230 ℃, reacting for 5 minutes, fully expanding and stripping graphite sheets into graphene nano sheets when the energy consumption per unit mass of built-in ultrasonic vibration reaches 5 kWh/kg, and obtaining a dispersion liquid containing uniformly dispersed graphene;
s33, preparing a decrosslinked emulsion: 100 parts by mass of waste latex is placed into graphene dispersion liquid obtained in the step S32, placed into a microwave reaction kettle (output power is 1000W), and heated to 190 ℃ under the stirring state, and reacted for 10 minutes to obtain decrosslinked latex;
s34, preparing a polylactic acid composite material: and (3) drying the uncrosslinked latex obtained in the step (S33) until the moisture is lower than 0.1%, uniformly mixing the uncrosslinked latex with 1000 parts by mass of polylactic acid, and sequentially putting the uncrosslinked latex into a high-speed mixer (the temperature is 80-100 ℃) and a continuous internal mixer (the temperature is 140-210 ℃) for melt blending, thereby obtaining the high-strength and high-toughness polylactic acid composite material after the energy consumption per unit mass reaches 1.5 kWh/kg.
Example 4
The invention provides a preparation method of a cross-linked waste latex reinforced and toughened polylactic acid composite material, which comprises the following steps:
s41, preparing an intercalation expandable graphite solution: adding 2 parts by mass of expandable graphite and 0.03 part by mass of stripping agent (sodium dodecyl sulfate) into 100 parts by mass of water, uniformly stirring, shearing, grinding and dispersing by a pipeline shearing, dispersing and emulsifying machine, and obtaining a dispersion liquid of the stripping agent uniformly coating the expandable graphite after the energy consumption per unit mass reaches 5 kWh/kg;
s42, preparing graphene dispersion liquid: placing the dispersion liquid obtained in the step S41 into a microwave reaction kettle (with the output power of 3000W), heating to 240 ℃, reacting for 6 minutes, fully expanding and stripping graphite sheets into graphene nano sheets when the energy consumption per unit mass of built-in ultrasonic vibration reaches 10 kWh/kg, and obtaining a dispersion liquid containing uniformly dispersed graphene;
s43, preparing a decrosslinked emulsion: placing 500 parts by mass of waste latex into the graphene dispersion liquid obtained in the step S42, placing into a microwave reaction kettle (output power is 2000W), heating to 170 ℃ under a stirring state, and reacting for 12 minutes to obtain the decrosslinked latex;
s44, preparing a polylactic acid composite material: and (3) drying the uncrosslinked latex obtained in the step (S43) until the moisture is lower than 0.1%, uniformly mixing the uncrosslinked latex with 7000 parts by mass of polylactic acid, and sequentially putting the uncrosslinked latex into a screw kneader (the temperature is 90-120 ℃) and a single screw extruder (the temperature is 180-240 ℃) for melt blending, thereby obtaining the high-strength and high-toughness polylactic acid composite material after the energy consumption per unit mass reaches 3 kWh/kg.
Example 5
The invention provides a preparation method of a cross-linked waste latex reinforced and toughened polylactic acid composite material, which comprises the following steps:
s51, preparing an intercalation expandable graphite solution: adding 3 parts by mass of expandable graphite and 0.025 part by mass of stripping agent (sodium dodecyl sulfate) into 100 parts by mass of water, uniformly stirring, shearing, grinding and dispersing by a shearing, emulsifying and homogenizing machine, and obtaining a dispersion liquid of the stripping agent uniformly coating the expandable graphite after the energy consumption per unit mass reaches 8 kWh/kg;
s52, preparing graphene dispersion liquid: placing the dispersion liquid obtained in the step S51 into a microwave reaction kettle (with the output power of 4000W), heating to 250 ℃, reacting for 4 minutes, fully expanding and stripping graphite sheets into graphene nano sheets when the energy consumption per unit mass of built-in ultrasonic vibration reaches 6 kWh/kg, and obtaining a dispersion liquid containing uniformly dispersed graphene;
s53, preparing a decrosslinked emulsion: 2500 parts by mass of waste latex is placed into the graphene dispersion liquid obtained in the step S52, placed into a microwave reaction kettle (the output power is 3500W), and heated to 195 ℃ under the stirring state, and reacted for 7 minutes to obtain the decrosslinked latex;
s54, preparing a polylactic acid composite material: and (3) drying the uncrosslinked latex obtained in the step (S53) until the moisture is lower than 0.1%, uniformly mixing the uncrosslinked latex with 25000 parts by mass of polylactic acid, and putting the mixture into a continuous internal mixer for melt blending (the processing temperature is 160-230 ℃), so that the high-strength and high-toughness polylactic acid composite material is obtained after the energy consumption per unit mass reaches 2.2 kWh/kg.
Comparative example 1 (no uncrosslinking reaction on waste latex)
The polylactic acid composite material is prepared basically by adopting the method of the example 1, except that the waste latex is not treated in the example, but 500 parts by mass of the waste latex and 500 parts by mass of polylactic acid are directly and uniformly mixed, and the mixture is placed into a reciprocating screw extruder for melt blending (the processing temperature is 120-195 ℃), and after the energy consumption per unit mass reaches 0.1 kWh/kg, the polylactic acid composite material is obtained.
Comparative example 2 (direct microwave-assisted uncrosslinked waste latex without graphene incorporation)
The method of example 2 is basically adopted to prepare the uncrosslinked waste latex and the polylactic acid composite material filled with the same, except that graphene nano sheets are not introduced in the method, but the waste latex is directly subjected to microwave-assisted uncrosslinking reaction, namely 250 parts by mass of waste latex is placed into a microwave reaction kettle (output power is 5000W), and the temperature is raised to 220 ℃ under the stirring state, and the reaction is carried out for 30 seconds, so as to obtain the uncrosslinked latex; and (3) uniformly mixing the obtained uncrosslinked latex with 250 parts by mass of polylactic acid, and placing the mixture into a turnover internal mixer for melt blending (the processing temperature is 240-265 ℃), wherein after the energy consumption per unit mass reaches 5 kWh/kg, the polylactic acid composite material is obtained.
Comparative example 3 (introduction of Expandable graphite alone, microwave assisted uncrosslinking of waste latex)
The method of example 3 is basically adopted to prepare the uncrosslinked waste latex and the polylactic acid composite material filled with the same, except that the expandable graphite is only adopted to improve the dielectric property of the waste latex in the example, namely, 1 part by mass of the expandable graphite and 100 parts by mass of the waste latex are added into 100 parts by mass of water, and after being stirred uniformly, the mixture is placed into a microwave reaction kettle (output power 1000W), and the temperature is raised to 190 ℃ under the stirring state, and the reaction is carried out for 10 minutes, so as to obtain the uncrosslinked latex; and (3) drying the obtained uncrosslinked latex, uniformly mixing the dried uncrosslinked latex with 1000 parts by mass of polylactic acid, and sequentially placing the mixture into a high-speed mixer (the temperature is 80-100 ℃) and a continuous internal mixer (the temperature is 140-210 ℃) for melt blending, thereby obtaining the polylactic acid composite material after the energy consumption per unit mass reaches 1.5 kWh/kg.
Structural characterization and performance testing:
the quenching section micro-morphology of example 1 and the quenching section micro-morphology of comparative example 1 were observed by a field emission Scanning Electron Microscope (SEM), and the results thereof are shown in fig. 3 and 4;
the mechanical properties and the electrical conductivity of the composite materials obtained in examples 1 to 5 and comparative examples 1 to 3 were tested, and the results are shown in Table 1. The performance evaluation method and the test standard are as follows: the extruded pelletized composite material was dried at 100 ℃ for 1-2 hours, and then the test samples (each set of samples comprised of 5 tensile test bars, 5 impact test bars, and 3 volume resistivity test boards) were molded using an injection molding machine equipped with standard test bar dies.
Mechanical property test: the obtained composite material is subjected to injection molding (the molding temperature is 160-220 ℃) to obtain a tensile and impact spline, and the tensile property of the composite material is tested by using a universal stretcher (model 5900) of Instron company in the United states according to the tensile property test standard of plastics in ASTM D638-2003 of the American society for testing materials; the impact properties of the composite materials were tested according to ASTM D256-1997 Standard test method for Izod impact Properties detection of plastics from the American society for testing materials. At least 3 parallel test samples were secured for each group and the results averaged.
Electrical performance testing: the surface resistance and the volume resistivity of the composite material are tested according to the national standard GB/T1410-2006 test method for volume resistivity and surface resistivity of solid insulation materials. At least 5 replicates per group were tested and the results averaged.
TABLE 1 test results of mechanical and electrical Properties of composite Material
Also significant is that examples 1-5 simultaneously exhibit good antistatic properties with a surface resistance of 1.0X10 due to the introduction of fully exfoliated, uniformly dispersed graphene nanoplatelets 8 ~9.9×10 12 In the omega range, and volume resistivity of 1.0X10 7 ~9.9×10 11 In the range of Ω & m, is excellent in anti-staticAn electrical material. In particular, example 2 has a surface resistance as low as 2X 10 8 Omega, and volume resistivity as low as 5X 10 7 Omega.m, the extremely small amount of graphene nano sheets can ensure the better electrical property of the composite material in a uniformly dispersed state. However, comparative examples 1 to 3 all show an insulating state and cannot be used as an antistatic material.
The foregoing is merely a preferred embodiment of the invention, and it should be noted that modifications could be made by those skilled in the art without departing from the principles of the invention, which modifications would also be considered to be within the scope of the invention.
Claims (10)
1. The preparation method of the uncrosslinked waste latex reinforced and toughened polylactic acid composite material is characterized by comprising the following steps of:
s1, preparing an intercalation expandable graphite solution: adding the expandable graphite and the stripping agent into water, stirring, and then placing the mixture into a liquid-phase circulating high-speed shearing and grinding device for shearing, grinding and dispersing to obtain a stripping agent coated expandable graphite dispersion liquid;
s2, preparing graphene dispersion liquid: placing the dispersion liquid obtained in the step S1 into a microwave reaction kettle, heating to 200-260 ℃ under ultrasonic oscillation, and reacting for 2-10 minutes to obtain graphene dispersion liquid;
s3, preparing a decrosslinked emulsion: placing the waste latex into the graphene dispersion liquid obtained in the step S2, placing the graphene dispersion liquid into a microwave reaction kettle, heating to 150-220 ℃, and reacting for 30 seconds-20 minutes to obtain the uncrosslinked latex;
s4, preparing a polylactic acid composite material: and (3) drying the uncrosslinked latex obtained in the step (S3), mixing with polylactic acid, and placing into a melt blending device for melt blending to obtain the polylactic acid composite material.
2. The method of manufacturing according to claim 1, characterized in that: the fixed carbon content of the expandable graphite in the step S1 is 90% -99.9%, and the size of the graphite flake is 5μm~1500 μm, the mass fraction of the m in the aqueous solution is 0.5% -5%.
3. The method of manufacturing according to claim 1, characterized in that: the stripping agent in the step S1 is at least one of polyvinylpyrrolidone, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl sulfonate, polyoxyethylene octyl phenol ether-10 and octyl phenol polyoxyethylene ether, and the mass fraction of the stripping agent is 1/200-1/50 of that of the expandable graphite.
4. The method of manufacturing according to claim 1, characterized in that: the liquid-phase circulation high-speed shearing and grinding equipment in the step S1 is at least one of a shearing and emulsifying homogenizer, a pipeline shearing and dispersing emulsifier, a vacuum homogenizing and emulsifying machine, a rod pin type sand mill and a turbine type sand mill, and the unit mass energy consumption in the grinding and dispersing process is 0.5-10 kWh/kg.
5. The method of manufacturing according to claim 1, characterized in that: the output power of the microwave reaction kettle in the step S2 is 200-5000W, and the energy consumption per unit mass of ultrasonic vibration is 1-20 kWh/kg.
6. The method of manufacturing according to claim 1, characterized in that: and in the step S3, the output power of the microwave reaction kettle is 200-5000W, and the mass ratio of the graphene to the waste latex is 1/1000-1/50.
7. The method of manufacturing according to claim 1, characterized in that: in the step S4, the uncrosslinked latex obtained in the step S3 is dried until the moisture is lower than 0.1%.
8. The method of manufacturing according to claim 1, characterized in that: the melt blending equipment in the step S4 is at least one of an open mill, a turnover internal mixer, a continuous internal mixer, a reciprocating screw extruder, a double screw extruder, a single screw extruder, a Z-type kneader, a screw kneader and a vacuum kneader, the processing temperature is 80-265 ℃, the energy consumption per unit mass in the melt blending process is 0.1-5 kWh/kg, and the mass ratio of the uncrosslinked latex to the polylactic acid is 1:19-1:1.
9. A polylactic acid composite material obtained by the preparation method according to any one of claims 1 to 8.
10. The polylactic acid composite according to claim 9, wherein: the tensile strength of the polylactic acid composite material is 50-70 MPa, and the impact toughness is 8-30 kJ/m 2 The surface resistance was 1.0X10 8 ~9.9×10 12 Omega, volume resistivity of 1.0X10 7 ~9.9×10 11 Ω·m。
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