CN111673941A - Plastic master batch preparation process - Google Patents

Plastic master batch preparation process Download PDF

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Publication number
CN111673941A
CN111673941A CN202010521618.8A CN202010521618A CN111673941A CN 111673941 A CN111673941 A CN 111673941A CN 202010521618 A CN202010521618 A CN 202010521618A CN 111673941 A CN111673941 A CN 111673941A
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modified
preparation process
parts
fiber
mixing
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蔡壮林
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Jiangxi Fushangmei Technology Co ltd
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Jiangxi Fushangmei Technology Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/002Methods
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/22Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04Homopolymers or copolymers of ethene
    • C08J2323/06Polyethene
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04Homopolymers or copolymers of ethene
    • C08J2423/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2497/00Characterised by the use of lignin-containing materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/265Calcium, strontium or barium carbonate
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • C08K3/041Carbon nanotubes
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/34Silicon-containing compounds
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/34Silicon-containing compounds
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/06Elements
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/22Expanded, porous or hollow particles
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/02Ingredients treated with inorganic substances
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    • C08K9/04Ingredients treated with organic substances
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/08Ingredients agglomerated by treatment with a binding agent

Abstract

The invention discloses a preparation process of plastic master batches, which relates to the field of plastic master batches and comprises the following steps: s1 preparing raw materials; s2, adding the polyoxyethylene fatty acid ester into water, adding the carbon nano tubes and the carbon nano fibers, and sanding; ultrasonic treatment and centrifugal sedimentation; s3, mixing and grinding the modified mica powder, the modified sepiolite powder, the modified quartz sand and the modified nano calcium carbonate to obtain a second mixture; s4, adding the modified lignin fiber and the modified polyvinyl alcohol fiber into absolute ethyl alcohol respectively, and performing ultrasonic dispersion; s5, melting and blending the ethylene-vinyl acetate copolymer and the first mixed solution to obtain a mixed material A; s6, mixing the polyethylene, the butyl stearate and the second mixture to obtain a mixed material B; s7, mixing polyethylene, butyl stearate, modified lignin fiber and modified polyvinyl alcohol fiber to obtain a mixed material C; s8 blending and extruding the mixed material A, B and C. The invention has the advantages of improving the mechanical property of the plastic master batch, having conductivity and antistatic property.

Description

Plastic master batch preparation process
Technical Field
The invention relates to the field of plastic master batches, in particular to a preparation process of plastic master batches.
Background
The master batch is a granular material prepared by mixing and milling various required additives, fillers and a small amount of carrier resin in the plastic processing and forming process for convenience in operation, and performing the processing processes of metering, mixing, melting, extruding, granulating and the like by using equipment such as an extruder, and is called master batch. The master batch consists of carrier resin, various fillers and various auxiliaries. The limit of the auxiliary agent or the content of the filler in the master batch is several times to dozens of times higher than the required amount in the actual plastic product. In the forming process, the proportion of the master batch and the matrix resin is adjusted according to the content of relevant components in the master batch and the required addition amount in an actual product. The masterbatch can be generally classified into common filler masterbatch (abbreviated as filler masterbatch) and functional masterbatch, such as masterbatch and anti-fogging masterbatch.
Generally, plastic products are insulators, i.e. they are not conductive, but in more and more practical applications, plastic products are required to have certain conductivity, for example, conductive plastic can be a material with good antistatic property, or an electromagnetic wave shielding material. In the prior art, the conductive plastics can be classified into structural conductive plastics and composite conductive plastics according to the manufacturing method of the conductive plastics, and the structural polymer conductive materials mainly comprise: (1) pi conjugated polymer: such as polyacetylene, (Sr) n, linear polyphenyl, layered high polymers, etc.; (2) metal chelate complexes: such as polyketone phthalocyanines; (3) charge-transfer type polymer complex: such as polycations, CQ complexes. Generally, the production cost of the polymer materials is high, the process difficulty is large, and the mass production is not available up to now. The conductive polymer materials widely used in the prior art are generally composite polymer materials, and the filling materials mainly comprise a metal dispersion system, a carbon black system and an organic complex dispersion system; among them, the metal dispersion is often difficult to pass through a filter unit in a plastic melt-based process after being filled in a matrix, resulting in an excessive pressure of the filter, often failing to be produced normally or having an excessive production cost.
Disclosure of Invention
The invention aims to at least solve one of the technical problems in the prior art and provides a preparation process of plastic master batch.
The technical solution of the invention is as follows:
a preparation process of plastic master batches comprises the following steps:
s1, preparing the following raw materials in parts by weight: 30-40 parts of polyethylene, 20-30 parts of ethylene-vinyl acetate copolymer, 10-16 parts of carbon nano tube, 5-10 parts of carbon nanofiber, 2-6 parts of modified sepiolite powder, 2-6 parts of modified mica powder, 1-5 parts of modified quartz sand, 2-6 parts of modified nano calcium carbonate, 1-5 parts of modified lignin fiber, 1-5 parts of modified polyvinyl alcohol fiber, 1-3 parts of butyl stearate and 2-3 parts of fatty acid polyoxyethylene ester;
s2, adding polyoxyethylene fatty acid into water, heating at 50-55 ℃ until the polyoxyethylene fatty acid is dissolved, continuously adding carbon nanotubes and carbon nanofibers, stirring to completely wet the carbon nanotubes and the carbon nanofibers to obtain a first mixed solution, adding the first mixed solution into a sand mill, and sanding for 20-30 min; then, carrying out ultrasonic treatment on the first mixed solution after sanding, wherein the ultrasonic power is 200-300 w, and the treatment time is 30-100 min; finally, centrifugally settling the first mixed solution after ultrasonic treatment to remove undispersed agglomerated particles;
s3, mixing the modified mica powder, the modified sepiolite powder, the modified quartz sand and the modified nano calcium carbonate, adding the mixture into a ball mill, and grinding for 30-60 min to obtain a second mixture;
s4, adding the modified lignin fiber into absolute ethyl alcohol, and carrying out ultrasonic dispersion for 5-10 minutes; adding the modified polyvinyl alcohol fiber into absolute ethyl alcohol, and carrying out ultrasonic dispersion for 5-10 minutes;
s5, adding the ethylene-vinyl acetate copolymer and the first mixed solution obtained in the step S2 into a torque rheometer for melt blending, wherein the blending temperature is 250-260 ℃, the screw rotating speed is 80-100 r/min, and the mixing time is 20-30 min, so that a mixed material A is obtained;
s6, adding the polyethylene, the butyl stearate and the second mixture obtained in the step S3 into a high-speed mixer, heating to 250-280 ℃, and mixing at a rotating speed of 1500-1800 r/min for 10-15 min to obtain a mixed material B;
s7, adding polyethylene, butyl stearate and the modified lignin fiber and the modified polyvinyl alcohol fiber in the step S3 into a high-speed mixer, heating to 230-250 ℃, and mixing at the rotating speed of 1200-1500 r/min for 10-15 min to obtain a mixed material C;
and S8, adding the mixed material A, the mixed material B and the mixed material C into a double-screw extruder, blending and extruding, cutting into particles, and drying at 90-100 ℃ to obtain the plastic master batch.
Preferably, the step S2 further includes: and taking out the first mixed solution after the ultrasonic treatment, placing the first mixed solution in an ice water bath for cooling and defoaming, and continuing the next ultrasonic treatment after the defoaming is finished.
Preferably, in the step S2, the number of times of the ultrasonic treatment is 4 to 8, and the time of each ultrasonic treatment is 4 to 5 min. .
Preferably, in the step S2, the centrifugal rate in the centrifugal sedimentation is 2500-3000 r/min, and the centrifugal time is 20-30 min.
Preferably, the preparation method of the modified sepiolite powder comprises the following steps: putting sepiolite into hydrochloric acid according to the solid-liquid ratio of 1g: 15-20 mL, stirring for 2-3 hours at 70-80 ℃, cooling to room temperature, filtering, washing, drying and grinding to obtain sepiolite powder; adding fatty alcohol-polyoxyethylene ether into deionized water, dissolving, adding sepiolite powder, uniformly mixing, adjusting the pH value to 7-8, and stirring for 3-4 hours at 70-80 ℃.
Preferably, the preparation method of the modified mica powder comprises the following steps: adding mica powder into distilled water, placing in ice water bath, adding concentrated hydrochloric acid while stirring, and dripping TiCl4Continuously adding the ammonium sulfate solution into the solution, mixing and stirring, heating the mixture to 90-100 ℃ in a water bath, and preserving heat for 30-60 min; then dropwise adding the prepared ammonia water solution until the pH value is 7, filtering, washing and drying at the temperature of 80 ℃ to obtain the modified mica powder.
Preferably, in step S1, the method for preparing the modified quartz sand includes: adding absolute ethyl alcohol into quartz sand, stirring uniformly, continuously adding nitric acid with the mass fraction of 70%, stirring for 2-4 h at 150-155 ℃, filtering, and drying for 2-3h at 120 ℃ to obtain the modified quartz sand.
Preferably, the preparation method of the modified nano calcium carbonate comprises the following steps: adding nano calcium carbonate and urea into distilled water, slowly adding 0.2mol/L titanium sulfate solution at 95-105 ℃ under the stirring condition until the dropwise adding is completed, adding a surfactant, reacting for 30-60 min, and drying at 70-75 ℃ for 10-14 h.
Preferably, the preparation method of the modified lignin fiber comprises the following steps: mixing the lignin fiber with absolute ethyl alcohol, performing ultrasonic dispersion for 10-15 min, slowly adding vinyl triethoxysilane, uniformly mixing, adjusting the pH to 7-7.5, stirring at a constant temperature of 50-55 ℃ for 15-25 h, cooling to room temperature, centrifuging, and performing vacuum drying at 70-75 ℃ to obtain the modified lignin fiber.
Preferably, the preparation method of the modified polyvinyl alcohol fiber comprises the following steps: mixing polyvinyl alcohol fibers with absolute ethyl alcohol, dispersing for 10-15 min by ultrasonic waves, continuing to soak in nitric acid for 2-4 h at 100-105 ℃, fishing out after soaking, and placing in a drying oven for drying; adding vinyltriethoxysilane into deionized water, adding the dried polyvinyl alcohol fiber, uniformly mixing, adjusting the pH to 7-7.5, stirring at a constant temperature of 60-65 ℃ for 10-20 h, cooling to room temperature, centrifuging, and drying in vacuum at 80-85 ℃ to obtain the modified polyvinyl alcohol fiber.
The invention has at least one of the following beneficial effects:
1. the invention adopts the carbon nano tube and the carbon nanofiber as the conductive filler, the carbon nano tube is a one-dimensional quantum material with the radial dimension of nanometer magnitude and the axial dimension of micrometer magnitude, and both ends of the tube are basically sealed, the carbon nano tube has excellent conductivity, and the conductivity can reach 1 ten thousand times of that of copper. Because the carbon nanotube has a very large aspect ratio (i.e. the ratio of length to diameter), when the carbon nanotube and the carbon nanofiber are dispersed in the matrix resin, the carbon nanotube is equivalent to a bridge and is carried in a gap between the carbon nanofibers, and by utilizing the excellent conductivity of the carbon nanotube and the carbon nanofiber, more conductive paths are formed in the matrix resin, more electrons flow, the resistivity is reduced, and the conductivity is improved. In addition, the carbon nano tube has good mechanical property, the tensile strength reaches 50-200 GPa, the hardness of the carbon nano tube is equivalent to that of diamond, and the carbon nano tube has a very large length-diameter ratio and is an ideal high-strength fiber material, so the carbon nano tube is called as a super fiber. The nano carbon fiber also has good thermal conductivity, lubricity, elasticity, adsorption property and strength property, and the nano carbon fiber has extremely short length and good flexibility, so that the nano carbon fiber can not be broken when being used as a filler and mixed with matrix resin, and the height-diameter ratio of the nano carbon fiber can be maintained, so that the mechanical property of the plastic master batch can be improved by adding the carbon nano tube and the nano carbon fiber into the matrix resin.
2. According to the invention, the lignin fiber and the polyvinyl alcohol fiber are added and modified, so that impurities on the surfaces of the lignin fiber and the polyvinyl alcohol fiber can be removed, the impurities are prevented from forming a weak bonding interface in the subsequent plastic master batch preparation process, the dispersibility of the lignin fiber and the polyvinyl alcohol fiber can be improved, the modified lignin fiber and the modified polyvinyl alcohol fiber can be uniformly dispersed in carrier resin, and external load is transferred to the lignin fiber and the polyvinyl alcohol fiber with higher strength from a matrix under the action of external force. Through the combined action of the lignin fiber, the polyvinyl alcohol fiber, the carbon nano tube and the carbon nano fiber, the external load can be effectively eliminated, and the toughness of the carrier resin is improved, so that the toughness of the plastic master batch is improved; the four fibers are matched with each other, so that the four fibers can be uniformly dispersed in the carrier resin, and the four fibers synergistically improve the toughness of the plastic master batch.
3. The invention adds mica powder, sepiolite powder, quartz sand and nano calcium carbonate into the plastic master batch raw material, wherein the mica powder is a non-metallic mineral and contains a plurality of components, wherein SiO is mainly contained in the mica powder2And Al2O3The mica powder has the characteristics of good elasticity, toughness, insulativity, high temperature resistance, acid and alkali resistance, corrosion resistance, strong adhesive force and the like, so that the mechanical property, the heat resistance, the insulativity and the chemical stability of a plastic product can be improved by adding the mica powder into the plastic master batch raw material, the glossiness of the surface of the plastic product can be increased, the aging of the plastic product is prevented, and the application field of the plastic product is expanded. The nano calcium carbonate can improve the rheological property of the plastic master batch and improve the formability of the plastic master batch; and has the functions of toughening and reinforcing, and can improve the bending strength, the bending elastic modulus, the thermal deformation temperature and the dimensional stability of the plastic. The sepiolite is a water-containing magnesium-rich silicate clay mineral with a layer chain structure, can increase the glossiness of master batches, and improves the mechanical property, heat resistance and the like of plastic products. Quartz sand is a silicate mineral that is hard, wear resistant, and chemically stable. The color of the quartz sand is milky white or colorless and semitransparent, the glossiness of the master batch can be increased, and the mechanical property, the heat resistance and the like of the plastic product are improved. The invention also carries out modification treatment on mica powder, sepiolite powder, quartz sand and nano calcium carbonate, firstly, TiCl is adopted4Treating mica powder with ammonium sulfate, TiCl4And ammonium sulfate to generate titanium dioxide, and the titanium dioxide and mica powder react to generate a mica powder/titanium dioxide composite material; reacting urea with titanium sulfate to generate titanium dioxide, and modifying the surface of the titanium dioxide with nano calcium carbonate; oxidation of hydrogen dioxideThe titanium has good glossiness, strong dispersibility, large covering power and weather resistance and antibacterial effect, so that the mechanical property, stability and surface glossiness of the plastic product can be improved by modifying the mica powder and the nano calcium carbonate and by the synergistic effect of the titanium dioxide, the mica powder and the nano calcium carbonate, the plastic product has the ultraviolet ray shielding and antibacterial effects, and the service life of the plastic product is prolonged. Secondly, the quartz sand is treated by nitric acid, so that gullies on the surface of the quartz sand can be increased and deepened, and the surface roughness of the quartz sand is improved, so that the mechanical engagement degree of the quartz sand and the resin matrix is improved; the sepiolite is processed by hydrochloric acid and fatty alcohol-polyoxyethylene ether, so that the surface area of the sepiolite is increased, the dispersibility of the sepiolite is improved, and the polarity of the sepiolite, the compatibility of the sepiolite and a resin matrix and the intermolecular force are increased by processing the sepiolite by the fatty alcohol-polyoxyethylene ether. The added modified mica powder, modified sepiolite powder, modified quartz sand, modified nano calcium carbonate and carrier resin have a synergistic enhancement effect, and can improve the tensile strength, impact strength, bending strength, elongation at break and the like of the plastic master batch.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
A preparation process of plastic master batches comprises the following steps:
s0, weighing the following raw materials in parts by weight: 30 parts of polyethylene, 20 parts of ethylene-vinyl acetate copolymer, 10 parts of carbon nano tube, 5 parts of carbon nano fiber, 2 parts of sepiolite, 2 parts of mica powder, 1 part of quartz sand, 2 parts of nano calcium carbonate, 1 part of lignin fiber, 1 part of polyvinyl alcohol fiber, 1 part of butyl stearate and 2 parts of polyoxyethylene fatty acid ester;
s1, putting the sepiolite into hydrochloric acid according to the solid-liquid ratio of 1g:15mL, stirring for 3 hours at 70 ℃, cooling to room temperature, filtering, washing, drying and grinding to obtain sepiolite powder; adding 0.1g of fatty alcohol-polyoxyethylene ether into 100g of deionized water, dissolving, adding sepiolite powder, uniformly mixing, adjusting the pH value to 7, and stirring at 70 ℃ for 4 hours to obtain the modified sepiolite powder.
Adding 10g of mica powder into 40mL of distilled water, placing the mixture in an ice-water bath condition, adding 3mL of concentrated hydrochloric acid while stirring, and dripping 8mL of TiCl with the concentration of 2mol/L4Continuing adding 8mL of 2mol/L ammonium sulfate solution, mixing and stirring, heating the mixture to 90 ℃ in a water bath, and preserving heat for 30 min; then adjusting the pH of the mixed solution to 7 by ammonia water, filtering, washing and drying at 80 ℃ to obtain the modified mica powder.
Adding 20mL of absolute ethyl alcohol into 10g of quartz sand, uniformly stirring, continuously adding 15mL of nitric acid with the mass fraction of 70%, stirring for 2h at 150 ℃, filtering, and drying for 2h at 120 ℃ to obtain the modified quartz sand.
Adding 1g of nano calcium carbonate and 8g of urea into 50mL of distilled water, slowly adding 4mL of titanium sulfate solution with the concentration of 0.2mol/L at 95 ℃ under the stirring condition until the dropwise addition is completed, adding 0.0015g of sodium dodecyl benzene sulfonate, reacting for 60min, and drying at 70 ℃ for 14h to obtain the modified nano calcium carbonate.
Mixing 1g of lignin fiber with 8mL of absolute ethyl alcohol, performing ultrasonic dispersion for 10min, slowly adding 0.8mL of vinyltriethoxysilane, uniformly mixing, adjusting the pH to 7, stirring at a constant temperature of 50 ℃ for 15h, cooling to room temperature, centrifuging, and performing vacuum drying at 70 ℃ to obtain the modified lignin fiber.
Mixing 1g of polyvinyl alcohol fiber with 8mL of absolute ethyl alcohol, performing ultrasonic dispersion for 10min, continuously adding 4mL of 65% nitric acid, soaking at 100 ℃ for 4h, taking out after soaking, and drying in a drying oven at 80 ℃; adding 2mL of vinyltriethoxysilane into deionized water, adding the dried polyvinyl alcohol fiber, uniformly mixing, adjusting the pH to 7, stirring at a constant temperature of 60 ℃ for 20h, cooling to room temperature, centrifuging, and drying in vacuum at 80 ℃ to obtain the modified polyvinyl alcohol fiber.
S2, adding fatty acid polyoxyethylene ester into 50 parts of water, heating at 50 ℃ until the fatty acid polyoxyethylene is dissolved, continuously adding carbon nano tubes and nano carbon fibers, stirring to completely wet the carbon nano tubes and the nano carbon fibers to obtain a first mixed solution, adding the first mixed solution into a sand mill, and sanding for 20 min; then carrying out ultrasonic treatment on the first mixed solution after sanding, carrying out ultrasonic treatment for eight times with the ultrasonic power of 200w, wherein the ultrasonic treatment time is 4min each time, taking out the first mixed solution after each treatment is finished, placing the first mixed solution in an ice water bath for cooling and defoaming, and continuing the next ultrasonic treatment after the defoaming is finished; finally, centrifugally settling the first mixed solution subjected to ultrasonic treatment, wherein the centrifugal rate is 2500r/min, the centrifugal time is 30min, and removing undispersed agglomerated particles;
s3, mixing the modified mica powder, the modified sepiolite powder, the modified quartz sand and the modified nano calcium carbonate, adding the mixture into a ball mill, and grinding for 30min to obtain a second mixture;
s4, adding the modified lignin fiber into absolute ethyl alcohol, and carrying out ultrasonic dispersion for 5 minutes; adding the modified polyvinyl alcohol fiber into absolute ethyl alcohol, and carrying out ultrasonic dispersion for 5 minutes;
s5, adding the ethylene-vinyl acetate copolymer and the first mixed solution obtained in the step S2 into a torque rheometer for melt blending, wherein the blending temperature is 250 ℃, the screw rotation speed is 100r/min, and the mixing time is 30min, so as to obtain a mixed material A;
s6, adding the polyethylene, the butyl stearate and the second mixture obtained in the step S3 into a high-speed mixer, heating to 250 ℃, and mixing for 15min at the rotating speed of 1500r/min to obtain a mixed material B;
s7, adding polyethylene, butyl stearate and the modified lignin fiber and the modified polyvinyl alcohol fiber obtained in the step S3 into a high-speed mixer, heating to 230 ℃, and mixing for 15min at the rotating speed of 1200r/min to obtain a mixed material C;
and S8, adding the mixed material A, the mixed material B and the mixed material C into a double-screw extruder, blending and extruding, granulating, and drying at 90 ℃ to obtain the plastic master batch.
Example 2
A preparation process of plastic master batches comprises the following steps:
s0, weighing the following raw materials in parts by weight: 32 parts of polyethylene, 22 parts of ethylene-vinyl acetate copolymer, 12 parts of carbon nano tube, 6 parts of carbon nano fiber, 3 parts of sepiolite, 3 parts of mica powder, 2 parts of quartz sand, 3 parts of nano calcium carbonate, 2 parts of lignin fiber, 2 parts of polyvinyl alcohol fiber, 1.5 parts of butyl stearate and 2.2 parts of polyoxyethylene fatty acid ester;
s1, putting the sepiolite into hydrochloric acid according to the solid-liquid ratio of 1g:18mL, stirring for 2.5 hours at the temperature of 75 ℃, cooling to room temperature, filtering, washing, drying and grinding to obtain sepiolite powder; adding 0.15g of fatty alcohol-polyoxyethylene ether into 100g of deionized water, dissolving, adding sepiolite powder, uniformly mixing, adjusting the pH value to 7.5, and stirring at 75 ℃ for 3.5 hours to obtain the modified sepiolite powder.
Adding 10g of mica powder into 45mL of distilled water, placing the mixture in an ice-water bath condition, adding 4mL of concentrated hydrochloric acid while stirring, and dripping 9mL of TiCl with the concentration of 2mol/L4Continuing adding 9mL of 2mol/L ammonium sulfate solution, mixing and stirring, heating the mixture to 95 ℃ in a water bath, and keeping the temperature for 45 min; then adjusting the pH of the mixed solution to 7 by ammonia water, filtering, washing and drying at 85 ℃ to obtain the modified mica powder.
Adding 20mL of absolute ethyl alcohol into 10g of quartz sand, uniformly stirring, continuously adding 18mL of nitric acid with the mass fraction of 70%, stirring for 3h at 152 ℃, filtering, and drying for 2-3h at 120 ℃ to obtain the modified quartz sand.
Adding 1g of nano calcium carbonate and 9g of urea into 50mL of distilled water, slowly adding 5mL of titanium sulfate solution with the concentration of 0.2mol/L at 100 ℃ under the stirring condition until the dropwise addition is finished, adding 0.002g of sodium dodecyl benzene sulfonate, reacting for 45min, and drying at 72 ℃ for 124h to obtain the modified nano calcium carbonate.
Mixing 1g of lignin fiber with 9mL of absolute ethanol, performing ultrasonic dispersion for 12min, slowly adding 1mL of vinyltriethoxysilane, uniformly mixing, adjusting the pH to 7.2, stirring at a constant temperature of 52 ℃ for 50h, cooling to room temperature, centrifuging, and performing vacuum drying at 72 ℃ to obtain the modified lignin fiber.
Mixing 1g of polyvinyl alcohol fiber with 9mL of absolute ethyl alcohol, performing ultrasonic dispersion for 12min, continuously adding 5mL of 65% nitric acid, soaking at 102 ℃ for 3h, taking out after soaking, and drying in a drying oven at 80 ℃; adding 2mL of vinyltriethoxysilane into deionized water, adding the dried polyvinyl alcohol fiber, uniformly mixing, adjusting the pH to 7.2, stirring at a constant temperature of 62 ℃ for 15h, cooling to room temperature, centrifuging, and drying in vacuum at 82 ℃ to obtain the modified polyvinyl alcohol fiber.
S2, adding polyoxyethylene fatty acid into water, heating at 51 ℃ until the polyoxyethylene fatty acid is dissolved, continuously adding carbon nano tubes and carbon nano fibers, stirring to completely wet the carbon nano tubes and the carbon nano fibers to obtain a first mixed solution, adding the first mixed solution into a sand mill, and sanding for 22 min; then carrying out ultrasonic treatment on the first mixed solution after sanding, wherein ultrasonic treatment is carried out for seven times with the ultrasonic power of 220w, the ultrasonic treatment time is 4.5min each time, after each treatment is finished, the first mixed solution is taken out and placed in an ice-water bath for cooling and defoaming, and the next ultrasonic treatment is continued after the defoaming is finished; finally, centrifugally settling the first mixed solution subjected to ultrasonic treatment, wherein the centrifugation speed is 2600r/min, and the centrifugation time is 28min, and removing undispersed agglomerated particles;
s3, mixing the modified mica powder, the modified sepiolite powder, the modified quartz sand and the modified nano calcium carbonate, adding the mixture into a ball mill, and grinding for 40min to obtain a second mixture;
s4, adding the modified lignin fiber into absolute ethyl alcohol, and performing ultrasonic dispersion for 6 minutes; adding the modified polyvinyl alcohol fiber into absolute ethyl alcohol, and performing ultrasonic dispersion for 6 minutes;
s5, adding the ethylene-vinyl acetate copolymer and the first mixed solution obtained in the step S2 into a torque rheometer for melt blending, wherein the blending temperature is 252 ℃, the screw rotation speed is 85r/min, and the mixing time is 22min, so that a mixed material A is obtained;
s6, adding the polyethylene, the butyl stearate and the second mixture obtained in the step S3 into a high-speed mixer, heating to 260 ℃, and mixing for 11min at a rotating speed of 1600r/min to obtain a mixed material B;
s7, adding polyethylene, butyl stearate and the modified lignin fiber and the modified polyvinyl alcohol fiber obtained in the step S3 into a high-speed mixer, heating to 235 ℃, and mixing for 11min at the rotating speed of 1300r/min to obtain a mixed material C;
and S8, adding the mixed material A, the mixed material B and the mixed material C into a double-screw extruder, blending and extruding, cutting into granules, and drying at 95 ℃ to obtain the plastic master batch.
Example 3
S0, weighing the following raw materials in parts by weight: 35 parts of polyethylene, 25 parts of ethylene-vinyl acetate copolymer, 14 parts of carbon nano tube, 7 parts of carbon nanofiber, 4 parts of sepiolite, 4 parts of mica powder, 3 parts of quartz sand, 4 parts of nano calcium carbonate, 3 parts of lignin fiber, 3 parts of polyvinyl alcohol fiber, 2 parts of butyl stearate and 2.5 parts of polyoxyethylene fatty acid ester;
s1, putting the sepiolite into hydrochloric acid according to the solid-liquid ratio of 1g:20mL, stirring for 2 hours at 80 ℃, cooling to room temperature, filtering, washing, drying and grinding to obtain sepiolite powder; adding 0.2g of fatty alcohol-polyoxyethylene ether into 100g of deionized water, dissolving, adding sepiolite powder, uniformly mixing, adjusting the pH value to 8, and stirring for 3 hours at 80 ℃ to obtain the modified sepiolite powder.
Adding 10g of mica powder into 50mL of distilled water, placing the mixture in an ice-water bath condition, adding 1mL of concentrated hydrochloric acid while stirring, and dripping 10mL of TiCl with the concentration of 2mol/L4Continuously adding 10mL of 2mol/L ammonium sulfate solution, mixing and stirring, heating the mixture to 90-100 ℃ in a water bath, and preserving heat for 30-60 min; then adjusting the pH of the mixed solution to 7 by ammonia water, filtering, washing and drying at 80 ℃ to obtain the modified mica powder.
Adding 20mL of absolute ethyl alcohol into 10g of quartz sand, uniformly stirring, continuously adding 20mL of nitric acid with the mass fraction of 70%, stirring for 4h at 155 ℃, filtering, and drying for 3h at 120 ℃ to obtain the modified quartz sand.
Adding 1g of nano calcium carbonate and 10g of urea into 50mL of distilled water, slowly adding 6mL of titanium sulfate solution with the concentration of 0.2mol/L at 105 ℃ under the stirring condition until the dropwise addition is completed, adding 0.0025g of sodium dodecyl benzene sulfonate, reacting for 60min, and drying at 75 ℃ for 14h to obtain the modified nano calcium carbonate.
Mixing 1g of lignin fiber with 10mL of absolute ethanol, performing ultrasonic dispersion for 15min, slowly adding 1.5mL of vinyltriethoxysilane, uniformly mixing, adjusting the pH to 7.5, stirring at the constant temperature of 55 ℃ for 15h, cooling to room temperature, centrifuging, and performing vacuum drying at the temperature of 70-75 ℃ to obtain the modified lignin fiber.
Mixing 1g of polyvinyl alcohol fiber with 10mL of absolute ethyl alcohol, performing ultrasonic dispersion for 15min, continuously adding 5mL of 65% nitric acid, soaking at 105 ℃ for 2h, taking out after soaking, and drying in a drying oven at 80 ℃; adding 2.5mL of vinyl triethoxysilane into deionized water, adding the dried polyvinyl alcohol fiber, uniformly mixing, adjusting the pH to 7.5, stirring at a constant temperature of 65 ℃ for 10h, cooling to room temperature, centrifuging, and drying in vacuum at 85 ℃ to obtain the modified polyvinyl alcohol fiber.
S2, adding polyoxyethylene fatty acid into water, adding polyoxyethylene fatty acid at 53 ℃ until the polyoxyethylene fatty acid is dissolved, continuously adding carbon nano tubes and carbon nano fibers, stirring to completely wet the carbon nano tubes and the carbon nano fibers to obtain a first mixed solution, adding the first mixed solution into a sand mill, and sanding for 25 min; then carrying out ultrasonic treatment on the first mixed solution after sanding, carrying out ultrasonic treatment for six times with the ultrasonic power of 250w, wherein the ultrasonic treatment time is 4.5min each time, taking out the first mixed solution after each treatment is finished, placing the first mixed solution in an ice water bath for cooling and defoaming, and continuing the next ultrasonic treatment after the defoaming is finished; finally, centrifugally settling the first mixed solution subjected to ultrasonic treatment, wherein the centrifugal rate is 2700r/min, the centrifugal time is 25min, and removing undispersed agglomerated particles;
s3, mixing the modified mica powder, the modified sepiolite powder, the modified quartz sand and the modified nano calcium carbonate, adding the mixture into a ball mill, and grinding for 45min to obtain a second mixture;
s4, adding the modified lignin fiber into absolute ethyl alcohol, and performing ultrasonic dispersion for 8 minutes; adding the modified polyvinyl alcohol fiber into absolute ethyl alcohol, and performing ultrasonic dispersion for 8 minutes;
s5, adding the ethylene-vinyl acetate copolymer and the first mixed solution obtained in the step S2 into a torque rheometer for melt blending, wherein the blending temperature is 255 ℃, the screw rotation speed is 90r/min, and the mixing time is 25min, so that a mixed material A is obtained;
s6, adding the polyethylene, the butyl stearate and the second mixture obtained in the step S3 into a high-speed mixer, heating to 265 ℃, and mixing for 13min at the rotating speed of 1650r/min to obtain a mixed material B;
s7, adding polyethylene, butyl stearate and the modified lignin fiber and the modified polyvinyl alcohol fiber obtained in the step S3 into a high-speed mixer, heating to 2400 ℃, and mixing at the rotating speed of 1300r/min for 13min to obtain a mixed material C;
and S8, adding the mixed material A, the mixed material B and the mixed material C into a double-screw extruder, blending and extruding, cutting into granules, and drying at 95 ℃ to obtain the plastic master batch.
Example 4
S0, weighing the following raw materials in parts by weight: 38 parts of polyethylene, 28 parts of ethylene-vinyl acetate copolymer, 15 parts of carbon nano tube, 9 parts of carbon nanofiber, 5 parts of sepiolite, 5 parts of mica powder, 4 parts of quartz sand, 5 parts of nano calcium carbonate, 4 parts of lignin fiber, 4 parts of polyvinyl alcohol fiber, 2.8 parts of butyl stearate and 2.8 parts of polyoxyethylene fatty acid ester;
s1, same as example 3;
s2, adding polyoxyethylene fatty acid into water, adding polyoxyethylene fatty acid at 54 ℃ until the polyoxyethylene fatty acid is dissolved, continuously adding carbon nano tubes and carbon nano fibers, stirring to completely wet the carbon nano tubes and the carbon nano fibers to obtain a first mixed solution, adding the first mixed solution into a sand mill, and sanding for 28 min; then carrying out ultrasonic treatment on the first mixed solution after sanding, carrying out ultrasonic treatment for five times with ultrasonic power of 280w, wherein the ultrasonic treatment time is 5min each time, taking out the first mixed solution after each treatment is finished, placing the first mixed solution in an ice water bath for cooling and defoaming, and continuing the next ultrasonic treatment after the defoaming is finished; finally, centrifugally settling the first mixed solution subjected to ultrasonic treatment, wherein the centrifugal rate is 2900r/min, the centrifugal time is 22min, and removing undispersed agglomerated particles;
s3, mixing the modified mica powder, the modified sepiolite powder, the modified quartz sand and the modified nano calcium carbonate, adding the mixture into a ball mill, and grinding for 50min to obtain a second mixture;
s4, adding the modified lignin fiber into absolute ethyl alcohol, and performing ultrasonic dispersion for 9 minutes; adding the modified polyvinyl alcohol fiber into absolute ethyl alcohol, and performing ultrasonic dispersion for 90 minutes;
s5, adding the ethylene-vinyl acetate copolymer and the first mixed solution obtained in the step S2 into a torque rheometer for melt blending, wherein the blending temperature is 258 ℃, the screw rotation speed is 95r/min, and the mixing time is 28min, so as to obtain a mixed material A;
s6, adding polyethylene, butyl stearate and the second mixture obtained in the step S3 into a high-speed mixer, heating to 275 ℃, and mixing at a rotating speed of 1700r/min for 12min to obtain a mixed material B;
s7, adding polyethylene, butyl stearate and the modified lignin fiber and the modified polyvinyl alcohol fiber obtained in the step S3 into a high-speed mixer, heating to 245 ℃, and mixing at the rotating speed of 1400r/min for 12min to obtain a mixed material C;
and S8, adding the mixed material A, the mixed material B and the mixed material C into a double-screw extruder, blending and extruding, granulating, and drying at 100 ℃ to obtain the plastic master batch.
Example 5
S0, weighing the following raw materials in parts by weight: 40 parts of polyethylene, 30 parts of ethylene-vinyl acetate copolymer, 16 parts of carbon nano tube, 10 parts of carbon nanofiber, 6 parts of sepiolite, 6 parts of mica powder, 5 parts of quartz sand, 6 parts of nano calcium carbonate, 5 parts of lignin fiber, 5 parts of polyvinyl alcohol fiber, 3 parts of butyl stearate and 3 parts of polyoxyethylene fatty acid ester;
s1, same as example 3;
s2, adding polyoxyethylene fatty acid into water, adding polyoxyethylene fatty acid at 55 ℃ until the polyoxyethylene fatty acid is dissolved, continuously adding carbon nano tubes and carbon nano fibers, stirring to completely wet the carbon nano tubes and the carbon nano fibers to obtain a first mixed solution, adding the first mixed solution into a sand mill, and sanding for 30 min; then carrying out ultrasonic treatment on the first mixed solution after sanding, carrying out ultrasonic treatment for four times with the ultrasonic power of 300w, wherein the ultrasonic treatment time is 5min each time, taking out the first mixed solution after each treatment is finished, placing the first mixed solution in an ice water bath for cooling and defoaming, and continuing the next ultrasonic treatment after the defoaming is finished; finally, centrifugally settling the first mixed solution subjected to ultrasonic treatment at the centrifugal speed of 3000r/min for 20min, and removing undispersed agglomerated particles;
s3, mixing the modified mica powder, the modified sepiolite powder, the modified quartz sand and the modified nano calcium carbonate, adding the mixture into a ball mill, and grinding for 60min to obtain a second mixture;
s4, adding the modified lignin fiber into absolute ethyl alcohol, and performing ultrasonic dispersion for 10 minutes; adding the modified polyvinyl alcohol fiber into absolute ethyl alcohol, and performing ultrasonic dispersion for 10 minutes;
s5, adding the ethylene-vinyl acetate copolymer and the first mixed solution obtained in the step S2 into a torque rheometer for melt blending, wherein the blending temperature is 260 ℃, the screw rotation speed is 100r/min, and the mixing time is 30min, so as to obtain a mixed material A;
s6, adding the polyethylene, the butyl stearate and the second mixture obtained in the step S3 into a high-speed mixer, heating to 280 ℃, and mixing for 10min at the rotating speed of 1800r/min to obtain a mixed material B;
s7, adding polyethylene, butyl stearate and the modified lignin fiber and the modified polyvinyl alcohol fiber obtained in the step S3 into a high-speed mixer, heating to 250 ℃, and mixing at a rotating speed of 1500r/min for 10min to obtain a mixed material C;
and S8, adding the mixed material A, the mixed material B and the mixed material C into a double-screw extruder, blending and extruding, granulating, and drying at 100 ℃ to obtain the plastic master batch.
Comparative example 1
The process is the same as example 1 except that modified mica powder, modified sepiolite powder, modified quartz sand and modified nano calcium carbonate are not added.
Comparative example 2
In step S1, the mica powder, sepiolite powder, silica sand, and nano calcium carbonate were not modified, and the procedure was otherwise the same as in example 1.
Comparative example 3
Modified lignin fiber and modified polyvinyl alcohol fiber are not added. The rest is the same as example 1.
Comparative example 4
In step S1, the same procedure as in example 1 was repeated, except that the lignin fibers and the polyvinyl alcohol fibers were not modified.
Comparative example 5
The same procedure as in example 1 was repeated except that the carbon nanofibers were not used.
Comparative example 6
The procedure of example 1 was repeated except that the carbon nanotubes were not added.
Testing
The plastic master batches prepared in the examples 1-5 and the comparative examples 1-4 are respectively hot-pressed for 42min at 190 ℃ in a flat vulcanizing machine, and then cold-pressed for 4min and 4min at 30 ℃ to prepare a disk-shaped test sample with the diameter of 8cm and the thickness of 4mm, and the performance of the test sample is tested as follows:
(1) the main mechanical properties of the plastic sample strip are tested, and the test method and the standard are as follows: the test piece is characterized by comprising the following components of tensile strength GB/T1040-2006, elongation at break GB/T1040-2006, impact strength GB/T1843-2008 and bending strength GB/T9341-2000, wherein 5 plastic sample bars are taken for each group of test samples to be tested, and finally the average value is taken as the final test result. The test results are shown in table 1:
TABLE 1
Serial number Tensile strength/MPa Elongation at break/% Impact Strength/kJ.m2 Flexural Strength/MPa
Example 1 58.6 318 53.9 98.1
Example 2 59.9 325 54.5 102.3
Example 3 62..1 338 56.4 104.9
Example 4 61.2 321 55.9 103.5
Example 5 61.9 315 55.2 104.2
Comparative example 1 26.1 194 16.8 56.1
Comparative example 2 35.2 227 24.4 65.3
Comparative example 3 22.9 134 18.6 33.7
Comparative example 4 32.8 198 26.3 58.5
Comparative example 5 39.9 239 35.6 67.3
Comparative example 6 35.4 199 32.6 61.5
(2) According to the plastic resistivity test standard GB/T1410-2006, drying a wafer-shaped sample with the thickness of 8cm multiplied by 4mm, putting the dried sample into a high-impedance meter test box, adjusting the range of appropriate voltage and resistance value, carrying out volume resistance test, wherein the test voltage is 300-500V, and calculating the volume resistivity according to a formula rho ═ R × S/H, wherein R is a resistance test value, S is the effective area of the test sample, H is the thickness of the sample, and the test result is shown in Table 2:
TABLE 2
Serial number Volume resistivity/Ω · cm
Example 1 0.005
Example 2 0.006
Example 3 0.007
Example 4 0.007
Example 5 0.006
Comparative example 1 0.005
Comparative example 2 0.005
Comparative example 3 0.005
Comparative example 4 0.005
Comparative example 5 0.0018
Comparative example 6 0.001
As can be seen from Table 1, the plastic specimens obtained from the plastic master batches obtained in examples 1 to 5 all had good tensile strength, elongation at break, impact strength and flexural strength, and the tensile strength, elongation at break, impact strength and flexural strength of example 3 were the best. As can be seen from comparison of examples 1 to 5 with comparative examples 1 to 4, the tensile strength, elongation at break, impact strength and bending strength of the plastic sample bars injection-molded from the plastic master batches prepared in examples 1 to 5 are significantly superior to those of comparative example 1 (raw materials including no modified mica powder, modified sepiolite powder, modified quartz sand and modified nano calcium carbonate), comparative example 2 (raw materials including no modified lignin fiber and polyvinyl alcohol fiber), comparative example 3 (raw materials including no modified lignin fiber and modified polyvinyl alcohol fiber), comparative example 4 (step S1 including no modified lignin fiber and polyvinyl alcohol fiber), and comparative example 5 (raw materials including no nano carbon fiber), from which it can be seen whether nano carbon fiber, modified mica powder, modified sea powder, modified quartz sand, modified nano calcium carbonate, modified lignin fiber and modified polyvinyl alcohol fiber are added to the raw materials, and whether sepiolite powder, modified quartz sand, modified nano calcium carbonate, modified lignin fiber and modified polyvinyl alcohol fiber are added to the raw materials, The modification of sepiolite powder, quartz sand, nano calcium carbonate, lignin fiber and polyvinyl alcohol fiber can affect the tensile strength, elongation at break, impact strength and bending strength of the plastic master batch. According to the invention, appropriate raw materials of carbon nanofiber, carbon nanotube, mica powder, sepiolite powder, quartz sand, nano calcium carbonate, lignin fiber and polyvinyl alcohol fiber are selected to be matched with carrier resin, and the raw materials are modified, so that the mechanical property of the plastic master batch is improved, and a plastic sample strip formed by injection molding of the plastic master batch has good tensile strength, elongation at break, impact strength and bending strength.
As can be seen from Table 2, the volume resistivity of the plastic master batch prepared by the invention can reach 0.005 omega cm, and can reach 0.007 omega cm at most, and the plastic master batch has higher conductivity; comparing examples 1-5 with comparative examples 5-6, it can be seen that the volume resistivity of examples 1-5 is significantly greater than that of comparative example 5 (without carbon nanofibers) and comparative example 6 (without carbon nanotubes), and the volume resistivity of comparative example 5 (without carbon nanofibers) and comparative example 6 (without carbon nanotubes) is significantly less than that of comparative example 1, so it can be deduced that the invention adopts two fillers of carbon nanofibers and carbon nanotubes as conductive materials, the carbon nanofibers and carbon nanotubes have synergistic effect, and the conductivity of the plastic master batch is significantly reduced if one of the fillers is lacked.
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by equivalent exchanges or equivalent substitutions fall within the protection scope of the present invention.

Claims (10)

1. A preparation process of plastic master batches is characterized by comprising the following steps:
s1, preparing the following raw materials in parts by weight: 30-40 parts of polyethylene, 20-30 parts of ethylene-vinyl acetate copolymer, 10-16 parts of carbon nano tube, 5-10 parts of carbon nanofiber, 2-6 parts of modified sepiolite powder, 2-6 parts of modified mica powder, 1-5 parts of modified quartz sand, 2-6 parts of modified nano calcium carbonate, 1-5 parts of modified lignin fiber, 1-5 parts of modified polyvinyl alcohol fiber, 1-3 parts of butyl stearate and 2-3 parts of fatty acid polyoxyethylene ester;
s2, adding polyoxyethylene fatty acid into water, heating at 50-55 ℃ until the polyoxyethylene fatty acid is dissolved, continuously adding carbon nanotubes and carbon nanofibers, stirring to completely wet the carbon nanotubes and the carbon nanofibers to obtain a first mixed solution, adding the first mixed solution into a sand mill, and sanding for 20-30 min; then, carrying out ultrasonic treatment on the first mixed solution after sanding, wherein the ultrasonic power is 200-300 w, and the treatment time is 30-100 min; finally, carrying out centrifugal sedimentation on the first mixed solution after ultrasonic treatment to remove undispersed agglomerated particles;
s3, mixing the modified mica powder, the modified sepiolite powder, the modified quartz sand and the modified nano calcium carbonate, adding the mixture into a ball mill, and grinding for 30-60 min to obtain a second mixture;
s4, adding the modified lignin fiber into absolute ethyl alcohol, and carrying out ultrasonic dispersion for 5-10 minutes; adding the modified polyvinyl alcohol fiber into absolute ethyl alcohol, and carrying out ultrasonic dispersion for 5-10 minutes;
s5, adding the ethylene-vinyl acetate copolymer and the first mixed solution obtained in the step S2 into a torque rheometer for melt blending, wherein the blending temperature is 250-260 ℃, the screw rotating speed is 80-100 r/min, and the mixing time is 20-30 min, so that a mixed material A is obtained;
s6, adding the polyethylene, the butyl stearate and the second mixture obtained in the step S3 into a high-speed mixer, heating to 250-280 ℃, and mixing at a rotating speed of 1500-1800 r/min for 10-15 min to obtain a mixed material B;
s7, adding polyethylene, butyl stearate and the modified lignin fiber and the modified polyvinyl alcohol fiber in the step S4 into a high-speed mixer, heating to 230-250 ℃, and mixing at the rotating speed of 1200-1500 r/min for 10-15 min to obtain a mixed material C;
and S8, adding the mixed material A, the mixed material B and the mixed material C into a double-screw extruder, blending and extruding, cutting into particles, and drying at 90-100 ℃ to obtain the plastic master batch.
2. The preparation process of the plastic masterbatch according to claim 1, wherein the preparation process comprises the following steps: the step S2 further includes: and taking out the first mixed solution after the ultrasonic treatment, placing the first mixed solution in an ice water bath for cooling and defoaming, and continuing the next ultrasonic treatment after the defoaming is finished.
3. The preparation process of the plastic masterbatch according to claim 2, wherein the preparation process comprises the following steps: in the step S2, the ultrasonic treatment is performed for 4-8 times, and the time of each ultrasonic treatment is 4-5 min.
4. The preparation process of the plastic masterbatch according to claim 2, wherein the preparation process comprises the following steps: in the step S2, the centrifugal speed of centrifugal sedimentation is 2500-3000 r/min, and the centrifugal time is 20-30 min.
5. The preparation process of the plastic masterbatch according to claim 1, wherein the preparation process comprises the following steps: in the step S1, the preparation method of the modified sepiolite powder includes: putting sepiolite into hydrochloric acid according to the solid-liquid ratio of 1g: 15-20 mL, stirring for 2-3 hours at 70-80 ℃, cooling to room temperature, filtering, washing, drying and grinding to obtain sepiolite powder; adding fatty alcohol-polyoxyethylene ether into deionized water, dissolving, adding sepiolite powder, uniformly mixing, adjusting the pH value to 7-8, and stirring for 3-4 hours at 70-80 ℃.
6. The preparation process of the plastic masterbatch according to claim 1, wherein the preparation process comprises the following steps: in the step S1, the preparation method of the modified mica powder includes: adding mica powder into distilled water, placing in ice water bath, adding concentrated hydrochloric acid while stirring, and dripping TiCl4Continuously adding the ammonium sulfate solution into the solution, mixing and stirring, heating the mixture to 90-100 ℃ in a water bath, and preserving heat for 30-60 min; then dropwise adding the prepared ammonia water solution until the pH value is 7, filtering, washing and drying at the temperature of 80 ℃ to obtain the modified mica powder.
7. The preparation process of the plastic masterbatch according to claim 1, wherein the preparation process comprises the following steps: in the step S1, the preparation method of the modified quartz sand includes: adding absolute ethyl alcohol into quartz sand, stirring uniformly, continuously adding nitric acid with the mass fraction of 70%, stirring for 2-4 h at 150-155 ℃, filtering, and drying for 2-3h at 120 ℃ to obtain the modified quartz sand.
8. The preparation process of the plastic masterbatch according to claim 1, wherein the preparation process comprises the following steps: the preparation method of the modified nano calcium carbonate comprises the following steps: adding nano calcium carbonate and urea into distilled water, slowly adding 0.2mol/L titanium sulfate solution at 95-105 ℃ under the stirring condition until the dropwise adding is completed, adding a surfactant, reacting for 30-60 min, and drying at 70-75 ℃ for 10-14 h.
9. The preparation process of the plastic masterbatch according to claim 1, wherein the preparation process comprises the following steps: in step S1, the method for preparing the modified lignin fiber includes: mixing the lignin fiber with absolute ethyl alcohol, performing ultrasonic dispersion for 10-15 min, slowly adding vinyl triethoxysilane, uniformly mixing, adjusting the pH to 7-7.5, stirring at a constant temperature of 50-55 ℃ for 15-25 h, cooling to room temperature, centrifuging, and performing vacuum drying at 70-75 ℃ to obtain the modified lignin fiber.
10. The preparation process of the plastic masterbatch according to claim 1, wherein the preparation process comprises the following steps: in step S1, the method for preparing the modified polyvinyl alcohol fiber includes: mixing polyvinyl alcohol fibers with absolute ethyl alcohol, dispersing for 10-15 min by ultrasonic waves, continuously adding 65% nitric acid by mass, soaking for 2-4 h at 100-105 ℃, taking out after soaking, and placing in a drying oven for drying; adding vinyltriethoxysilane into deionized water, adding the dried polyvinyl alcohol fiber, uniformly mixing, adjusting the pH to 7-7.5, stirring at a constant temperature of 60-65 ℃ for 10-20 h, cooling to room temperature, centrifuging, and drying in vacuum at 80-85 ℃ to obtain the modified polyvinyl alcohol fiber.
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