CN113956652B - Antistatic master batch preparation method and antistatic master batch - Google Patents
Antistatic master batch preparation method and antistatic master batch Download PDFInfo
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- CN113956652B CN113956652B CN202111463260.9A CN202111463260A CN113956652B CN 113956652 B CN113956652 B CN 113956652B CN 202111463260 A CN202111463260 A CN 202111463260A CN 113956652 B CN113956652 B CN 113956652B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 application discloses an antistatic master batch preparation method, which comprises the following steps: s1, dissolving 15-25 parts by weight of nylon particles in 85-115 parts by weight of high-concentration formic acid solution, standing and filtering to obtain nylon/formic acid solution; s2, uniformly mixing 45-55 parts by weight of graphene oxide solution with 45-55 parts by weight of high-concentration formic acid solution, and performing ultrasonic treatment to obtain graphene oxide/formic acid solution; s3: slowly adding graphene oxide/formic acid solution into nylon/formic acid solution at normal temperature, and uniformly stirring to obtain nylon/graphene oxide/formic acid mixed solution; s4: and stirring the nylon/graphene oxide/formic acid mixed solution at a preset stirring speed, slowly adding 90-110 parts of ethanol in the stirring process to separate out nylon/graphene oxide, and filtering to obtain nylon/graphene oxide floccules.
Description
Technical Field
The application relates to the technical field of nylon recycling, in particular to an antistatic master batch preparation method and an antistatic master batch.
Background
Polyamide is commonly called Nylon (Nylon), and the English name Polyamide (PA) is a thermoplastic resin general term containing repeated amide groups- (NHCO) on a molecular main chain, and comprises aliphatic PA, aliphatic-aromatic PA and aromatic PA. The aliphatic PA has a large variety, high yield and wide application, and the naming of the aliphatic PA is determined by the specific carbon number of the synthetic monomer; was invented by the well-known chemist Carsephse in the United states and his scientific group.
With the mass application of plastics such as nylon, the plastic has recycling value after the service life is finished, and almost all thermoplastics have recycling value. The plastic recycling industry of China gradually flourishes the market and small and medium enterprises such as Yongquan appear after entering twenty-first century, and the plastic recycling industry is changed from a former small workshop type recycling mode to a commercial mode taking market demands as power, and is driven to be oriented towards market demands and prices; specifically, nylon 6, also called PA6, polyamide 6, nylon 6, is a high molecular compound; the nylon 6 is one of five general engineering plastics, has the characteristics of good mechanical property, aging resistance, abrasion resistance, dimensional stability and the like, and is widely applied to the fields of household appliances, automobile parts, chemical pipes and the like.
At present, two main methods for recycling thermoplastic plastics such as nylon 6 are available: a. the recycling process is simple and has small investment, but the added value of the recycled material is low, and the recycled material can be generally only used in a degrading way and is applied to some lower-end products; in addition, there are problems such as secondary recovery of the reclaimed materials. b. The nylon 6 molecular chain is cut off by alcoholysis and other methods, the molecular weight is reduced, and then the nylon is recovered and polymerized. The method can be used for recycling and obtaining nylon 6 materials with high molecular weight, high mechanical property and high purity, but the method has complex process and low productivity, so as to be beneficial to industrial utilization; the existing recovery method of thermoplastic plastics such as nylon 6 has the defects of complex process, low productivity, low recovery added value and the like.
Disclosure of Invention
In order to solve the technical problems, the application discloses an antistatic master batch preparation method, which is characterized in that a solution method is adopted to recover nylon materials, and the prepared graphene oxide/formic acid solution and nylon/formic acid solution are uniformly mixed, so that nylon can be well coated on the surface of graphene oxide, and then the nylon/graphene oxide antistatic master batch is prepared by adopting a water or alcohol precipitation method, so that nylon in nylon particles to be recovered is effectively utilized, the problem of difficult dispersion between graphene oxide and macromolecules is effectively solved, and the added value of nylon recovery is improved.
In order to achieve the above object, the present application provides a method for preparing an antistatic masterbatch, comprising the steps of:
s1, dissolving 15-25 parts by weight of nylon particles in 85-115 parts by weight of high-concentration formic acid solution, standing and filtering to obtain nylon/formic acid solution;
s2, uniformly mixing 45-55 parts by weight of graphene oxide solution with 45-55 parts by weight of high-concentration formic acid solution, and performing ultrasonic treatment to obtain graphene oxide/formic acid solution;
s3: slowly adding the graphene oxide/formic acid solution into the nylon/formic acid solution at normal temperature, and uniformly stirring to obtain a nylon/graphene oxide/formic acid mixed solution;
s4: stirring the nylon/graphene oxide/formic acid mixed solution at a preset stirring speed, slowly adding 900-1100 parts by weight of distilled water or 90-110 parts of ethanol in the stirring process to separate out nylon/graphene oxide, and filtering to obtain nylon/graphene oxide floccules;
s5: and (3) drying the nylon/graphene oxide floccules at 50-80 ℃, and grinding the dried nylon/graphene oxide floccules to obtain the antistatic master batch.
In some embodiments, the method of making the nylon particles comprises:
and crushing the nylon plastic to be recycled, cleaning and drying to obtain nylon particles.
In some embodiments, the dissolving 15-25 parts by weight of nylon particles in 85-115 parts by weight of high concentration formic acid solution, standing, filtering to obtain nylon/formic acid solution comprises:
adding 15-25 parts by weight of nylon particles into 85-115 parts by weight of high-concentration formic acid solution, mixing, stirring the solution for 4-6 hours at the temperature of 45-55 ℃ and the rotating speed of 1000-2000rpm until the nylon particles are completely dissolved in the formic acid solution, standing for 22-26 hours, and filtering out lower sediment in the solution to obtain nylon/formic acid solution.
In some embodiments, the graphene oxide solution is an aqueous graphene oxide solution having a graphene oxide content of 1% -3%;
the pH value of the graphene oxide solution is 4-7.
In some embodiments, the step of slowly adding the graphene oxide/formic acid solution into the nylon/formic acid solution, and uniformly stirring to obtain a nylon/graphene oxide/formic acid mixed solution comprises the following steps:
slowly adding the graphene oxide/formic acid solution into the nylon/formic acid solution, stirring the mixed solution at a rotating speed of 1000-2000rpm for 8-12min, and performing ultrasonic treatment for 10-20min to obtain a nylon/graphene oxide/formic acid mixed solution.
In some embodiments, the stirring the nylon/graphene oxide/formic acid mixed solution at a preset stirring speed, slowly adding 900-1100 parts of distilled water or 90-110 parts of ethanol during stirring to separate out nylon/graphene oxide floc, and filtering to obtain nylon/graphene oxide floc, including:
stirring the formic acid solution of nylon/graphene oxide at a rotating speed of 1000-2000rpm, slowly adding 1000 parts of distilled water or 100 parts of ethanol in the stirring process to separate out nylon/graphene oxide, and filtering to obtain nylon/graphene oxide floccules.
In some embodiments, the drying treatment is performed on the nylon/graphene oxide floccule at 50-80 ℃, and the grinding treatment is performed on the dried nylon/graphene oxide floccule to obtain an antistatic master batch, which comprises:
and (3) drying the nylon/graphene oxide floccules at 60-70 ℃ for 3.5-4.5 hours until the weight of the nylon/graphene oxide floccules reaches constant, grinding the dried nylon/graphene oxide floccules, and screening out particles with the particle size of less than or equal to 10 meshes to obtain the antistatic master batch.
In some embodiments, the nylon particles are nylon 6;
the concentration of the high-concentration formic acid solution is more than or equal to 90 percent.
The application also provides an antistatic master batch, which is prepared by the antistatic target preparation method;
the antistatic master batch is used for mixing with a nylon material, extruding and injection molding to obtain the nylon composite material.
The application also provides a preparation method of the nylon composite material, which comprises the following steps:
physically mixing 1-10 parts by weight of antistatic master batch with 90-99 parts by weight of nylon chips, and shaking uniformly to obtain nylon chips with the surface adsorbed with the antistatic master batch, wherein the antistatic master batch is the antistatic master batch;
and extruding and injection molding the nylon slices adsorbed with the antistatic master batch by adopting a screw at 230-250 ℃ to obtain the nylon composite material.
The implementation of the embodiment of the application has the following beneficial effects:
according to the preparation method of the antistatic master batch, the nylon material is recovered by adopting a solution method, and the prepared graphene oxide/formic acid solution and the nylon/formic acid solution are uniformly mixed, so that the nylon can be better coated on the surface of the graphene oxide, and the nylon/graphene oxide antistatic master batch is prepared by adopting a water or alcohol precipitation method, so that the nylon in the nylon particles to be recovered is effectively utilized, the problem of difficult dispersion between the graphene oxide and a polymer is effectively solved, and the added value of nylon recovery is improved;
compared with the traditional preparation method of the antistatic master batch, the nylon/graphene oxide antistatic master batch prepared by the preparation method of the application is simple in process, easy to produce in batches and environment-friendly; the preparation method can ensure that the nylon recovery process is simple, and meanwhile, the nylon recovery material with high mechanical strength and high added value is realized.
Drawings
In order to more clearly illustrate the method for preparing an antistatic masterbatch and the antistatic masterbatch described herein, the drawings required for the embodiments will be briefly described below, and it will be apparent that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to the drawings without inventive effort for those of ordinary skill in the art.
Fig. 1 is an SEM schematic of an antistatic masterbatch according to example 3 of the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
The application provides a preparation method of an antistatic master batch, which comprises the following steps:
s1, dissolving 15-25 parts by weight of nylon particles in 85-115 parts by weight of high-concentration formic acid solution, standing and filtering to obtain nylon/formic acid solution;
s2, uniformly mixing 45-55 parts by weight of graphene oxide solution with 45-55 parts by weight of high-concentration formic acid solution, and performing ultrasonic treatment to obtain graphene oxide/formic acid solution;
s3: slowly adding the graphene oxide/formic acid solution into the nylon/formic acid solution at normal temperature, and uniformly stirring to obtain a nylon/graphene oxide/formic acid mixed solution;
s4: stirring the nylon/graphene oxide/formic acid mixed solution at a preset stirring speed, slowly adding 900-1100 parts by weight of distilled water or 90-110 parts of ethanol in the stirring process to separate out nylon/graphene oxide, and filtering to obtain nylon/graphene oxide floccules;
s5: and (3) drying the nylon/graphene oxide floccules at 50-80 ℃, and grinding the dried nylon/graphene oxide floccules to obtain the antistatic master batch.
The nylon material is recovered by the solution method, and the prepared graphene oxide/formic acid solution and the nylon/formic acid solution are uniformly mixed, so that the nylon can be better coated on the surface of the graphene oxide, and then the nylon/graphene oxide antistatic master batch is prepared by the water or alcohol precipitation method, so that the nylon in the nylon particles to be recovered is effectively utilized, the problem of difficult dispersion between the graphene oxide and the macromolecule is effectively solved, and the added value of nylon recovery is improved.
In the embodiment of the application, the nylon particles can be prepared by the following method; specifically, the method comprises the following steps: crushing nylon plastic to be recycled, and cleaning and drying the crushed product to obtain nylon particles; correspondingly, the recovered nylon particles can comprise a plurality of different colors, and the nylon particles with different colors can be selected and classified;
specifically, nylon particles of the same color may be used for dissolution treatment in one experiment.
Illustratively, the particle size of the nylon particles produced may be 2cm or less.
In the embodiment of the application, the high-concentration formic acid solution can be a formic acid solution with the concentration of more than 90%;
illustratively, in embodiments of the present application, the high concentration formic acid solution can be a 98% strength formic acid solution.
Nylon 6 particles can be adopted in the nylon, and when antistatic master batch preparation is carried out, nylon 6/formic acid solution, nylon 6/graphene oxide/formic acid mixed solution, nylon 6/graphene oxide floccule and the like are prepared.
Specifically, the recovered nylon 6 particles are dissolved by adopting a high-concentration formic acid solution, and the nylon 6/formic acid solution with higher purity can be obtained by purification;
in the embodiment of the application, 15-25 parts by weight of nylon 6 particles can be weighed and mixed with 85-115 parts by weight of high-concentration formic acid solution, the solution is stirred at the speed of 1000-2000rpm for 4-6 hours at the temperature of 45-55 ℃ until the nylon 6 particles are completely dissolved in the formic acid solution, the solution is allowed to stand for 22-26 hours to naturally settle, and the lower sediment in the solution is filtered to obtain the nylon 6/formic acid solution.
Specifically, the lower sediment may be an impurity insoluble in water and formic acid solution;
specifically, the lower sediment may be an inorganic filler;
exemplary inorganic fillers may include, but are not limited to, silica, bentonite.
In the embodiment of the application, 15-25 parts by weight of nylon 6 particles are weighed and mixed with 85-115 parts by weight of high-concentration formic acid solution, wherein 15-25 parts by weight of nylon 6 particles can be added into 85-115 parts by weight of formic acid solution for dissolution, and 85-115 parts by weight of formic acid solution can be poured into a reaction vessel filled with 15-25 parts by weight of nylon 6 particles; the manner of addition is not limited here; specifically, the high-concentration formic acid solution is adopted to carry out solution on the nylon 6 particles, so that the nylon 6 can be fully dissolved; and the lower layer impurity sedimentation is removed, which is beneficial to improving the purity of nylon 6.
In the embodiment of the application, when preparing the graphene oxide/formic acid solution, 45-55 parts by weight of the graphene oxide solution can be poured into 45-55 parts by weight of the high-concentration formic acid solution to be uniformly stirred, and ultrasonic treatment is performed for 10-20min to obtain the graphene oxide/formic acid solution; according to the preparation method, when the graphene oxide/formic acid solution is prepared, the graphene oxide solution is poured into the high-concentration formic acid solution, so that precipitation of graphene oxide in the mixing process can be effectively avoided; the adoption of ultrasonic treatment can lead the graphene oxide in the graphene oxide/formic acid solution to be dispersed more uniformly.
Specifically, the graphene oxide solution used in preparing the graphene oxide/formic acid solution may be a graphene oxide aqueous solution with a graphene oxide content of 1% -3%; specifically, the pH value of the graphene oxide solution is 4-7.
In this embodiment of the present application, at normal temperature, the graphene oxide/formic acid solution is slowly added into the nylon/formic acid solution, and the obtained nylon/graphene oxide/formic acid mixed solution may be: slowly adding the graphene oxide/formic acid solution into the nylon 6/formic acid solution, and uniformly stirring to obtain a nylon 6/graphene oxide/formic acid mixed solution;
specifically, it may include: slowly adding the graphene oxide/formic acid solution into the nylon 6/formic acid solution, stirring the mixed solution at a rotating speed of 1000-2000rpm for 8-12min at normal temperature, and performing ultrasonic treatment for 10-20min to obtain a nylon 6/graphene oxide/formic acid mixed solution; according to the preparation method, when the nylon 6/graphene oxide/formic acid mixed solution is prepared, the graphene oxide/formic acid solution is poured into the nylon 6/formic acid solution, so that the nylon 6 can be effectively prevented from being separated out in the mixing process;
the method comprises the steps of slowly adding graphene oxide/formic acid solution into nylon 6/formic acid solution, stirring the mixed solution at a rotating speed of 2000rpm for 10min at normal temperature, and carrying out ultrasonic treatment for 15min to obtain nylon 6/graphene oxide/formic acid mixed solution; the nylon 6 and the graphene oxide are respectively dissolved in the formic acid solution, and the nylon 6 and the graphene oxide are mixed and dispersed, so that the nylon 6 in the obtained nylon 6/graphene oxide/formic acid mixed solution is better coated on the surface of the graphene oxide molecule, and the problem of difficult dispersion between the graphene oxide and the macromolecule is effectively solved.
In the embodiment of the application, the nylon/graphene oxide/formic acid mixed solution is stirred at a preset stirring speed, 900-1100 parts of distilled water or 90-110 parts of ethanol is slowly added in the stirring process to separate out nylon/graphene oxide, and nylon/graphene oxide floccules are obtained through filtration; concentrating and recycling the filtered formic acid solution with smaller concentration to obtain formic acid solution with higher concentration; the recycling of the raw materials is realized, and the recycling environment-friendly chemical concept is met.
Specifically, the prepared nylon/graphene oxide floccules can be nylon 6/graphene oxide floccules;
specifically, the method for preparing nylon 6/graphene oxide floc is as follows: stirring a formic acid solution of nylon 6/graphene oxide at a rotating speed of 1000-2000rpm, slowly adding 1000 parts of distilled water or 100 parts of ethanol in the stirring process to separate out nylon 6/graphene oxide, and filtering to obtain nylon 6/graphene oxide floccules; wherein the nylon 6/graphene oxide floe may be light gray.
Further, nylon 6/graphene oxide floc may include two preparation methods:
the first preparation method can comprise the following steps: stirring the formic acid solution of the nylon 6/graphene oxide at a rotating speed of 1000-2000rpm, slowly adding 1000 parts of distilled water in the stirring process to separate out the nylon 6/graphene oxide, and filtering to obtain nylon 6/graphene oxide floccules.
Specifically, when distilled water is used for precipitation treatment of nylon 6/graphene oxide, in order to obtain nylon 6/graphene oxide floccules with higher states, a small amount of ethanol can be used for washing the obtained nylon 6/graphene oxide floccules, so that the nylon 6/graphene oxide is precipitated more fully; then drying treatment is carried out; thus, nylon 6/graphene oxide powdery master batch with higher purity can be obtained, namely the antistatic master batch; by adopting the way to precipitate, the cost is low, and nylon 6/graphene oxide floccules can be sufficiently precipitated.
The second preparation method can comprise the following steps: stirring a formic acid solution of nylon 6/graphene oxide at a rotating speed of 1000-2000rpm, slowly adding 100 parts of ethanol in the stirring process to separate out nylon 6/graphene oxide, and filtering to obtain nylon 6/graphene oxide floccules; the nylon 6/graphene oxide floccules are directly separated out by ethanol, so that the nylon 6/graphene oxide floccules are separated out more fully.
For example, the rotational speed in the above two preparation methods may be selected to be 2000rpm or 1500rpm.
In the embodiment of the present specification, when the antistatic master batch is prepared by using the nylon 6/graphene oxide floc obtained based on the two preparation methods, the following preparation methods may be adopted, which specifically may include: and (3) drying the nylon 6/graphene oxide floccules at 50-80 ℃ for 3.5-4.5 hours until the weight of the nylon 6/graphene oxide floccules reaches constant, grinding the dried nylon 6/graphene oxide floccules, and screening out particles with the particle size of less than or equal to 10 meshes to obtain the antistatic master batch.
Specifically, the drying treatment can be that nylon 6/graphene oxide floccules are placed in an oven at 60-70 ℃ for drying treatment.
For example, nylon 6/graphene oxide floccules can be dried at 60-70 ℃ for 4 hours until the weight of the nylon 6/graphene oxide floccules reaches constant, the dried nylon 6/graphene oxide floccules are ground, and particles with the particle size of less than or equal to 10 meshes are sieved to obtain the antistatic master batch.
In one embodiment of the application, the nylon 6 reclaimed material is used for preparing the antistatic master batch, and the raw material proportion and the preparation conditions in the preparation method comprise, but are not limited to, the raw material proportion and the preparation conditions in the following several embodiments;
example 1:
1) 15 parts by weight of nylon 6 particles are added into 100 parts of 98% formic acid solution, the mixture is stirred for 5 hours at the temperature of 45 ℃ and the rotating speed of 1000rpm until the nylon 6 particles are completely dissolved, the mixture is naturally settled for 24 hours, and the lower sediment is filtered to obtain nylon 6/formic acid solution;
2) Pouring 50 parts by weight of graphene oxide solution with the concentration of 1% into 50 parts by weight of 98% formic acid solution, uniformly mixing, and carrying out ultrasonic treatment for 10min to obtain graphene oxide/formic acid solution;
3) Slowly adding graphene oxide/formic acid solution into nylon 6/formic acid solution, stirring at normal temperature and 1000rpm for 10min, and performing ultrasonic treatment for 10min to obtain nylon 6/graphene oxide/formic acid mixed solution;
4) Stirring a formic acid solution of nylon 6/graphene oxide at a rotating speed of 1000rpm, slowly pouring 1000 parts of distilled water in the stirring process, separating out nylon 6/graphene oxide, and filtering to obtain nylon 6/graphene oxide floccules; then washing the nylon 6/graphene oxide floccules with a small amount of ethanol to obtain light gray nylon 6/graphene oxide floccules;
(5) Drying nylon 6/graphene oxide floccules in a 60 ℃ oven for 4 hours until the weight of the nylon 6/graphene oxide floccules is constant, grinding the nylon 6/graphene oxide floccules which are dried to be constant weight by adopting a grinding mill, and screening to obtain nylon 6/graphene oxide powdery master batch with the particle size of less than or equal to 10 meshes, namely an antistatic master batch;
specifically, the concentration of graphene oxide in the antistatic master batch prepared by the method is 3.3%; namely, the antistatic master batch is nylon 6 powdery master batch of 3.3% graphene oxide, and the antistatic master batch is expressed as antistatic master batch A in the subsequent use.
Example 2:
1) Adding 25 parts by weight of nylon 6 particles into 100 parts by weight of 98% formic acid solution, stirring at 2000rpm for 5 hours at 55 ℃ to completely dissolve the nylon 6 particles, naturally settling for 24 hours, and filtering out the sediment at the lower layer to obtain nylon 6/formic acid solution;
2) Pouring 50 parts by weight of graphene oxide solution with the concentration of 3% into 50 parts by weight of 98% formic acid solution, uniformly mixing, and carrying out ultrasonic treatment for 20min to obtain graphene oxide/formic acid solution;
3) Slowly adding graphene oxide/formic acid solution into nylon 6/formic acid solution, stirring at normal temperature and 2000rpm for 10min, and performing ultrasonic treatment for 20min to obtain nylon 6/graphene oxide/formic acid mixed solution;
4) Stirring a formic acid solution of nylon 6/graphene oxide at a rotating speed of 2000rpm, slowly pouring 100 parts of ethanol in the stirring process, separating out nylon 6/graphene oxide, and filtering to obtain nylon 6/graphene oxide floccules;
5) Drying nylon 6/graphene oxide floccules in a 70 ℃ oven for 4 hours until the weight of the nylon 6/graphene oxide floccules is constant, grinding the nylon 6/graphene oxide floccules which are dried to be constant weight by adopting a grinding mill, and screening to obtain nylon 6/graphene oxide powdery master batch with the particle size of less than or equal to 10 meshes, namely an antistatic master batch;
specifically, the concentration of graphene oxide in the antistatic master batch prepared by the method is 6%; namely, the antistatic master batch is nylon 6 powdery master batch of 6% graphene oxide, and the antistatic master batch is expressed as antistatic master batch B in the subsequent use.
Example 3
1) Adding 20 parts by weight of nylon 6 particles into 100 parts by weight of 98% formic acid solution, stirring for 5 hours at a speed of 2000rpm in an environment of 55 ℃ until the nylon 6 particles are completely dissolved, naturally settling for 24 hours, and filtering out the lower sediment to obtain nylon 6/formic acid solution;
2) Pouring 50 parts by weight of graphene oxide solution with the concentration of 2% into 50 parts by weight of 98% formic acid solution, uniformly mixing, and carrying out ultrasonic treatment for 20min to obtain graphene oxide/formic acid solution;
3) Slowly adding graphene oxide/formic acid solution into nylon 6/formic acid solution, stirring at normal temperature and 2000rpm for 10min, and performing ultrasonic treatment for 20min to obtain nylon 6/graphene oxide/formic acid mixed solution;
4) Stirring a formic acid solution of nylon 6/graphene oxide at a rotating speed of 2000rpm, slowly pouring 100 parts of ethanol in the stirring process, separating out nylon 6/graphene oxide, and filtering to obtain nylon 6/graphene oxide floccules;
5) Drying nylon 6/graphene oxide floccules in a 70 ℃ oven for 4 hours until the weight of the nylon 6/graphene oxide floccules is constant, grinding the nylon 6/graphene oxide floccules which are dried to be constant weight by adopting a grinding mill, and screening to obtain nylon 6/graphene oxide powdery master batch with the particle size of less than or equal to 10 meshes, namely an antistatic master batch;
specifically, the concentration of graphene oxide in the antistatic master batch prepared by the method is 5%; namely, the antistatic master batch is nylon 6 powdery master batch of 5% graphene oxide, and the antistatic master batch is expressed as antistatic master batch C in the subsequent use.
As shown in fig. 1, an SEM image of an antistatic masterbatch prepared by the method for preparing an antistatic masterbatch according to the present application; specifically, SEM images of antistatic master batches prepared by the preparation method in example 3; from the figure, it is evident that the wrinkled graphene oxide and nylon 6 are well coated, and the graphene oxide sheet is free.
According to the preparation method of the antistatic master batch disclosed by the application, the nylon 6/formic acid solution and the graphene oxide/formic acid solution which are respectively prepared from the formic acid solution are mixed and dispersed, so that the nylon 6 can be well coated on the surface of the graphene oxide, the problem of difficult dispersion between the graphene oxide and a polymer can be effectively solved, and when the nylon 6/graphene oxide is separated out by adopting distilled water or ethanol, the nylon 6/graphene oxide can be rapidly and fully separated out, the secondary aggregation of the graphene oxide is avoided, the recovered nylon 6 can be fully utilized, and the functionalization, high added value and diversification of the application field of the nylon 6 reclaimed material are realized.
The application also provides an antistatic master batch, which is prepared by adopting the preparation method of the antistatic master batch;
specifically, the antistatic master batch is at least used for mixing with a nylon material, extruding and injection molding to obtain a nylon composite material; wherein, the surface of the nylon composite material has good antistatic effect.
The application also provides a preparation method of the nylon composite material, which can comprise the following steps:
physically mixing 1-10 parts by weight of antistatic master batch with 90-99 parts by weight of nylon chips, and shaking uniformly to obtain nylon chips with the surface adsorbed with the antistatic master batch;
extruding and injection molding the nylon slices adsorbed with the antistatic master batch by adopting a screw rod at 230-250 ℃ to obtain a nylon composite material;
for example, a nylon slice adsorbed with the antistatic master batch can be extruded and injection molded by adopting a 240 ℃ double screw to obtain a nylon composite material;
in a specific embodiment, when the antistatic masterbatch is a nylon 6/graphene oxide powdery masterbatch, its preparation of the wood dragon 6 composite material may include, but is not limited to, the following several preparation methods;
the method comprises the following steps: physically mixing 5 parts by weight of antistatic master batch A with 95 parts by weight of nylon 6 slices, shaking uniformly, and enabling the nylon 6 slices to adsorb the antistatic master batch in an electrostatic adsorption mode;
adopting 240 ℃ double screws to extrude and mold nylon 6 slices with antistatic master batch adsorbed on the surfaces, and obtaining a nylon 6 composite material;
specifically, the graphene content in the nylon 6 composite material is 0.17%; the nylon 6 composite, denoted composite a, corresponds to example 4.
The second method is as follows: physically mixing 5 parts by weight of antistatic master batch B with 95 parts by weight of nylon 6 slices, shaking uniformly, and enabling the nylon 6 slices to adsorb the antistatic master batch in an electrostatic adsorption mode;
adopting 240 ℃ double screws to extrude and mold nylon 6 slices with antistatic master batch adsorbed on the surfaces, and obtaining a nylon 6 composite material;
specifically, the graphene content in the nylon 6 composite material is 0.3%; the nylon 6 composite, denoted composite B, corresponds to example 5.
And a third method: physically mixing 10 parts by weight of antistatic master batch B with 90 parts by weight of nylon 6 slices, shaking uniformly, and enabling the nylon 6 slices to adsorb the antistatic master batch in an electrostatic adsorption mode;
adopting 240 ℃ double screws to extrude and mold nylon 6 slices with antistatic master batch adsorbed on the surfaces, and obtaining a nylon 6 composite material;
specifically, the graphene content in the nylon 6 composite material is 0.5%; the nylon 6 composite, denoted composite C, corresponds to example 6.
To compare the volume resistivity of composite A, composite B and composite C obtained as described above; the volume resistivity of the composite material A, the volume resistivity of the composite material B and the volume resistivity of the composite material C are detected and calculated respectively by adopting a universal meter;
specifically, when calculating the volume resistivity of the composite material, the following calculation method may be adopted; taking a composite material A as an example for illustration:
cutting the composite material A into a cube A with L, W, H=11x1cm, and coating conductive adhesive on two surfaces of the cube A contacted with two copper sheet electrodes for detecting the resistor to reduce the contact resistance, thereby obtaining the resistor R 1 Then adopting the following calculation model to calculate the volume resistivity;
R A ＝R 1 * L is W/H wherein R A Representing the volume resistivity of composite a.
In the embodiment of the application, the volume resistivity R of the composite material B may be calculated by using the method for calculating the volume resistivity of the composite material a B Volume resistivity R of composite C C ；
Specifically, the specific data obtained by calculation are shown in table 1:
TABLE 1
| Experiment number | Example 4 | Example 5 | Example 6 |
| Sample numbering | Composite A | Composite material B | Composite C |
| Volume resistivity/Ω. cm | R A ＝3.37*10 6 | R B ＝1.82*10 6 | R C ＝8.56*10 5 |
Conclusion: as can be seen from the data in table 1, the volume resistivity of each of composite a, composite B and composite C is higher, and the higher the content of graphene oxide in the composite, the smaller the volume resistivity, and the better the conductivity.
In the present application, in order to verify the performance of the nylon composite material prepared by mixing the antistatic master batch prepared by the antistatic master batch preparation method of the present application with nylon;
specifically, to verify the performance of nylon 6 composites A, B and C, a set of comparative examples were set up;
comparative examples: wetting 25 parts by weight of 2% graphene oxide solution on 99.5 parts by weight of nylon 6 slices, coating graphene oxide on the surfaces of the nylon 6 slices by heating and evaporating a solvent, and extruding and injection molding by adopting a double screw at 240 ℃ to obtain a nylon 6 composite material; wherein the graphene content in the nylon 6 composite material is 0.5%, that is, the nylon 6 composite material is a composite material with the graphene content of 0.5%, and the nylon 6 composite material is denoted as a composite material D herein.
Specifically, the volume resistivity of the composite material D may be calculated by a calculation method of the volume resistivity of the composite material a, thereby obtaining the volume resistivity R of the composite material D D ；
Specifically, the comparative data are shown in table 2:
TABLE 2
| Experiment number | Example 6 | Comparative examples |
| Sample numbering | Composite C | Composite material D |
| Volume resistivity/Ω. cm | R C ＝8.56*10 5 | R D ＝5.90*10 8 |
Conclusion: as can be seen from the data in table 2, the volume resistivity of the composite material D obtained in the comparative example is significantly greater than that of the composite material C, which indicates that the dispersion of graphene oxide in the antistatic masterbatch prepared in the application is better, so that the additional value recovered by nylon 6 is higher.
Compared with the traditional preparation method of the antistatic master batch, the prepared graphene oxide/formic acid solution and nylon/formic acid solution are uniformly mixed, so that nylon can be better coated on the surface of graphene oxide, and the nylon/graphene oxide antistatic master batch is prepared by adopting a water precipitation method, so that the process is simple, batch production is easy, and the environment is protected; the preparation method can ensure that the nylon recovery process is simple, and meanwhile, the nylon recovery material with high mechanical strength and high added value is realized.
The foregoing disclosure is merely illustrative of a preferred embodiment of the present application and is not intended to limit the scope of the claims herein, as equivalent changes may be made in the claims herein without departing from the scope of the claims herein.
Claims (10)
1. A method for preparing an antistatic masterbatch, the method comprising the steps of:
s1, dissolving 15-25 parts by weight of nylon particles in 85-115 parts by weight of high-concentration formic acid solution, standing and filtering to obtain nylon/formic acid solution; wherein the concentration of the high-concentration formic acid solution is more than 90%;
s2, uniformly mixing 45-55 parts by weight of graphene oxide solution with 45-55 parts by weight of high-concentration formic acid solution, and performing ultrasonic treatment to obtain graphene oxide/formic acid solution; the graphene oxide solution is a graphene oxide aqueous solution with the graphene oxide content of 1% -3%;
s3: slowly adding the graphene oxide/formic acid solution into the nylon/formic acid solution at normal temperature, and uniformly stirring to obtain a nylon/graphene oxide/formic acid mixed solution;
s4: stirring the nylon/graphene oxide/formic acid mixed solution at a preset stirring speed, slowly adding 90-110 parts of ethanol in the stirring process to separate out nylon/graphene oxide, and filtering to obtain nylon/graphene oxide floccules;
s5: and (3) drying the nylon/graphene oxide floccules at 50-80 ℃, and grinding the dried nylon/graphene oxide floccules to obtain the antistatic master batch.
2. The method for preparing an antistatic master batch according to claim 1, wherein the method for preparing nylon particles comprises:
and crushing the nylon plastic to be recycled, cleaning and drying to obtain nylon particles.
3. The method for preparing an antistatic masterbatch according to claim 1 or 2, characterized in that step S1 comprises:
adding 15-25 parts by weight of nylon particles into 85-115 parts by weight of high-concentration formic acid solution, mixing, stirring the solution for 4-6 hours at the temperature of 45-55 ℃ and the rotating speed of 1000-2000rpm until the nylon particles are completely dissolved in the formic acid solution, standing for 22-26 hours, and filtering out lower sediment in the solution to obtain nylon/formic acid solution.
4. The process for preparing an antistatic masterbatch according to claim 1 wherein,
the pH value of the graphene oxide solution is 4-7.
5. The method for preparing an antistatic master batch according to claim 1, wherein step S3 comprises:
slowly adding the graphene oxide/formic acid solution into the nylon/formic acid solution, stirring the mixed solution at a rotating speed of 1000-2000rpm for 8-12min, and performing ultrasonic treatment for 10-20min to obtain a nylon/graphene oxide/formic acid mixed solution.
6. The method for preparing an antistatic master batch according to claim 1, wherein step S4 comprises:
stirring the nylon/graphene oxide/formic acid mixed solution at a rotating speed of 1000-2000rpm, slowly adding 100 parts of ethanol in the stirring process to separate out nylon/graphene oxide, and filtering to obtain nylon/graphene oxide floccules.
7. The method for preparing an antistatic master batch according to claim 1, wherein step S5 comprises:
and (3) drying the nylon/graphene oxide floccules at 60-70 ℃ for 3.5-4.5 hours until the weight of the nylon/graphene oxide floccules reaches constant, grinding the dried nylon/graphene oxide floccules, and screening out particles with the particle size of less than or equal to 10 meshes to obtain the antistatic master batch.
8. The method of preparing an antistatic masterbatch according to claim 1 wherein said nylon particles are nylon 6.
9. An antistatic master batch prepared by the method for preparing an antistatic master batch according to any one of claims 1 to 8;
the antistatic master batch is at least used for mixing with a nylon material, extruding and injection molding to obtain the nylon composite material.
10. The preparation method of the nylon composite material is characterized by comprising the following steps of:
physically mixing 1-10 parts by weight of antistatic master batch with 90-99 parts by weight of nylon chips, and shaking uniformly to obtain nylon chips with the surface adsorbed with the antistatic master batch, wherein the antistatic master batch is the antistatic master batch of claim 9;
and extruding and injection molding the nylon slices adsorbed with the antistatic master batch by adopting a screw at 230-250 ℃ to obtain the nylon composite material.
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