CN115746526A - Preparation method of graphene composite antistatic biodegradable PLA plastic - Google Patents
Preparation method of graphene composite antistatic biodegradable PLA plastic Download PDFInfo
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Abstract
The invention discloses a preparation method of a graphene composite antistatic biodegradable PLA plastic, which comprises the following steps: 1) Fully drying PLA granules, taking out the PLA granules, and dissolving the PLA granules in an organic solvent A to obtain a first mixture; 2) The Pd-diimine catalyst is used for catalyzing ethylene and 2- (trimethylsiloxy) ethyl acrylate to copolymerize to prepare HBPE @ OH; then HBPE @ OH is used as a macroinitiator, and the epoxy monomer epsilon-caprolactone is initiated by a hydroxyl end group to carry out graft copolymerization based on a ring-opening polymerization mechanism to obtain HBPE @ PCL; 3) Ultrasonically stripping graphite by utilizing HBPE @ PCL liquid phase to obtain a graphene dispersion liquid; 4) Adding the graphene dispersion liquid into the first mixture, and fully and uniformly stirring to obtain a second mixture; 5) And pouring and molding the second mixture, and removing the solvent to obtain the antistatic plastic. The antistatic property of the PLA plastic is obviously improved.
Description
Technical Field
The invention relates to a method for preparing antistatic plastic by utilizing biodegradable PLA.
Background
Polylactic Acid (PLA), a thermoplastic aliphatic polyester. Lactic acid or lactide required for producing polylactic acid can be obtained by fermentation, dehydration and purification of renewable resources, the obtained polylactic acid generally has good mechanical and processing properties, and the polylactic acid product can be rapidly degraded in various ways after being discarded.
The structure of lactic acid contains carboxyl and hydroxyl at the same time, so that esterification reaction can be carried out between lactic acid molecules to form a long chain. Although called polylactic acid, most of the carboxyl groups have been reacted in the polymerization reaction and there is practically no acidity, unlike polymers whose side groups are carboxyl groups represented by polyacrylic acid. The monomeric lactic acid of polylactic acid can be synthesized by chemical synthesis or by renewable resources. Generally, starch extracted from corn and cassava, sugar extracted from sugarcane and beet, cellulose extracted from straw and the like are used, and lactic acid is obtained through processes of fermentation, dehydration and the like. The lactic acid obtained needs to be purified to produce polylactic acid, because trace amounts of fumaric acid and acetic acid contained in lactic acid cause termination of the polymerization reaction.
The melting point, heat resistance, mechanical property and processability of polylactic acid are all related to the crystallinity of the polylactic acid, and the main factor influencing the crystallinity of the polylactic acid is the proportion of L-lactic acid and D-lactic acid in raw materials. If the starting material is pure L-lactic acid or pure D-lactic acid, the resulting poly-L-lactic acid (PLLA for short) is a highly crystalline polymer and poly-D-lactic acid (PDLA for short) is a semicrystalline polymer. The poly-L-lactic acid has a crystallinity of about 37%, a glass transition temperature of about 65 ℃, a melting point of 160 ℃, a tensile modulus of about 3 to 4GPa, and a flexural modulus of about 4 to 5GPa. Even if only a small amount of poly (D-lactic acid) is added, the crystallinity can be improved more. For example, after poly L-lactic acid is blended with poly D-lactic acid according to a certain proportion, the melting point of poly L-lactic acid can be increased by 50 ℃ at most, and the hot bending temperature is increased to about 170 ℃. The obtained heat-resistant polylactic acid has similar mechanical properties when used in an environment of 110 ℃ as compared with polystyrene and PETE, but can be continuously used at a much lower temperature, and the continuous use temperature can be increased after the crystallinity is increased, but the biodegradation rate is reduced. The polylactic acid can be vaporized into combustible gas by heating in a crucible.
Polylactic acid is partially hydrophobic relative to other biodegradable materials. The most preferred solvent for polylactic acid and copolymers of polylactic acid is chloroform. In addition, polylactic acid is soluble in chlorinated solvents, hot benzene, tetrahydrofuran and 1, 4-dioxane but insoluble in water, ethanol and most aliphatic hydrocarbon solvents
Generally, the most common method of preparing antistatic materials is to add an antistatic agent, but the mechanical properties of the resulting material are often significantly reduced by the addition of an antistatic agent, which may limit the applications of the product. In order to reduce the damage to the mechanical properties of the matrix material, carbonaceous materials and conductive polymers with excellent conductivity are often used to improve the antistatic properties of the matrix, such as flake graphite, carbon black, carbon nanotubes, graphene, multi-layer graphene, polyaniline (PANI), polypyrrole, etc., all of which are used as fillers to prepare antistatic composite materials. The structural characteristics of the filler also affect the performance of the antistatic composite.
Disclosure of Invention
The problem to be solved by the application is to provide a method for preparing antistatic plastic by using degradable plastic PLA, and improve the antistatic performance of the plastic.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a preparation method of a graphene composite antistatic biodegradable PLA plastic, which comprises the following steps:
1) Placing PLA granules in a blast oven for fully drying, taking out the PLA granules, and dissolving the PLA granules in an organic solvent A to obtain a first mixture;
2) The hyperbranched binary copolymer HBPE @ OH containing hydroxyl end groups is prepared by catalyzing ethylene and 2- (trimethylsiloxy) ethyl acrylate to copolymerize with Pd-diimine catalyst; then, taking hyperbranched binary copolymer HBPE @ OH as a macroinitiator, and initiating epoxy monomer epsilon-caprolactone (epsilon-CL) to graft and copolymerize based on a ring-opening polymerization mechanism through a hydroxyl end group to obtain polycaprolactone group grafted hyperbranched polyethylene HBPE @ PCL;
3) Utilizing polycaprolactone group grafted hyperbranched polyethylene HBPE @ PCL liquid phase ultrasonic stripping graphite to obtain graphene dispersion liquid;
4) Adding the graphene dispersion liquid obtained in the step 3) into the first mixture, and fully and uniformly stirring to obtain a second mixture; wherein the feeding ratio of the graphene to the PLA is 1:20-100 parts of;
5) Pouring and molding the second mixture obtained in the step 4), and removing the solvent to obtain the antistatic plastic.
In the present invention, PLA is commercially available, such as Natureworks/4060D, USA.
In the step 1), the organic solvent A needs to have good dissolving property for PLA and has a low boiling point and is easy to volatilize. Preferably, the organic solvent A is one or a mixture of more of chloroform, tetrahydrofuran and dichloromethane.
The Pd-diimine catalyst of the invention is preferably one of the following: the acetonitrile group Pd-diimine catalyst 1 and the methyl ester group-containing six-membered ring Pd-diimine catalyst 2 have the following structural formulas:
wherein, the first and the second end of the pipe are connected with each other,
both Pd-diimine catalysts can be synthesized in the laboratory with reference to the following references:
[1]Johnson L.K.,Killian C.M.,Brookhart M.J.Am.Chem.Soc.,1995,117,6414；[2]Johnson L.K.,Mecking S.,Brookhart M.J.Am.Chem.Soc.,1996,118,267.
the step 2) of the invention is specifically operated as follows: adding 2- (trimethylsiloxy) ethyl acrylate and an anhydrous solvent A into a reaction vessel under the protection of ethylene, controlling the temperature to be 15-35 ℃, then adding a Pd-diimine catalyst dissolved in the anhydrous solvent A, stirring and reacting for 12-48 hours under the conditions that the temperature is 15-35 ℃ and the ethylene pressure is 0.1-6 atm, pouring the obtained product into acidified methanol after the polymerization is finished to terminate the polymerization, and separating and purifying the obtained polymerization reaction mixture to obtain a hyperbranched binary copolymer HBPE @ OH containing hydroxyl end groups; adding hyperbranched binary copolymer HBPE @ OH, epsilon-CL, stannous octoate and anhydrous solvent B into a reaction container under the protection of nitrogen, controlling the temperature at 100-120 ℃ and the nitrogen pressure at 0.1-6 atm, stirring and reacting for 12-24 hours, placing the obtained product into liquid nitrogen for rapid cooling after the polymerization is finished to terminate the polymerization, adding excessive ethanol into the product, and separating and purifying the obtained polymerization reaction mixture to obtain polycaprolactone group grafted hyperbranched polyethylene HBPE @ PCL.
Preferably, in step 2), the anhydrous grade solvent A is selected from one of the following: anhydrous grade dichloromethane, trichloromethane or chlorobenzene.
Preferably, in step 2), the anhydrous grade solvent B is selected from one of the following: anhydrous grade toluene, xylene or ortho-dichlorobenzene.
Preferably, in the step 2), the mass amount of the Pd-diimine catalyst is 0.5-15.0 g/L (more preferably 10-15 g/L), and the mass amount of the 2- (trimethylsiloxy) ethyl acrylate is 0.2-1.0 mol/L (more preferably 0.4-0.6 mol/L), based on the total volume of the anhydrous grade solvent A; the mass usage of the HBPE @ OH is 10-15 g/L, the mass usage of the epsilon-CL is 100-250 g/L (more preferably 150-200 g/L), and the mass usage of the stannous octoate is 1-2.5 g/L (more preferably 1.5-2.0 g/L) based on the total volume of the anhydrous solvent B.
Preferably, in the step 2), the reaction temperature for synthesizing HBPE @ OH is 20-30 ℃, the ethylene pressure is 0.5-1.5atm, and the stirring reaction time is 20-30h; the reaction temperature for synthesizing HBPE @ PCL is 105-115 ℃, the nitrogen pressure is 0.5-1.5atm, and the stirring reaction time is 10-14h.
According to the preparation method, the preparation scheme of the graphene refers to CN103087335A, and the polycaprolactone group grafted hyperbranched binary copolymer HBPE @ PCL is used for preparing the graphene organic dispersion liquid. Specifically, step 3) of the present invention can be performed as follows: mixing graphite powder, an organic solvent B and a polycaprolactone group grafted hyperbranched binary copolymer HBPE @ PCL in proportion, wherein the organic solvent B is selected from one of the following chemical pure reagents or analytically pure reagents: tetrahydrofuran, chloroform, n-heptane, chlorobenzene, dichloromethane; and then carrying out ultrasonic treatment on the obtained mixture to obtain an initial graphene dispersion liquid, wherein the concentration of graphite powder is 0.1-1000 mg/mL, and the feeding mass ratio of HBPE @ PCL to graphite powder is 0.01-10: 1; further carrying out low-speed centrifugation and standing treatment to obtain a graphene dispersion liquid containing excessive HBPE @ PCL; and (3) carrying out ultrahigh-speed centrifugation or vacuum filtration on the obtained graphene dispersion liquid containing excessive HBPE @ PCL to remove the excessive HBPE @ PCL, and ultrasonically dispersing in the organic solvent B again to obtain the graphene organic dispersion liquid. Preferably, the obtained mixture is continuously subjected to ultrasonic treatment for 12-120 h under the conditions that the ultrasonic frequency is 80-100 Hz and the constant temperature is 15-35 ℃, so as to obtain the graphene initial dispersion liquid; centrifuging the graphene initial dispersion liquid for 25-60 min at room temperature under the condition of 2000-5000 rpm, standing for 10-60 min, and collecting a centrifugal supernatant liquid to obtain the graphene dispersion liquid containing excessive HBPE @ PCL. Preferably, the ultra-high speed centrifugation is carried out at 15 to 35 ℃ and 30000 to 50000 rpm. Preferably, the vacuum filtration is to carry out vacuum filtration on the graphene dispersion liquid containing excessive HBPE @ PCL by using a microfiltration membrane, wherein the average pore diameter of the microfiltration membrane is 0.01-0.05 μm, and the material is one of polytetrafluoroethylene, polyvinylidene fluoride or alumina.
In step 4) of the present invention, the stirring speed is preferably controlled to be 600 to 800rad/min, and the stirring time is preferably 30 to 60min.
In the step 5), graphene cannot be agglomerated in the process of removing the solvent, and the integrity of the PLA film is ensured, so that the film is formed in a normal-temperature closed container.
Compared with the prior art, the invention has the beneficial effects that:
1. the advantages of the antistatic plastic preparation are as follows: the antistatic material is prepared by adding the graphene prepared under the auxiliary stripping of the polycaprolactone grafted hyperbranched polyethylene into the biodegradable plastic PLA, so that the antistatic performance of the PLA can be greatly improved under the condition of small addition amount of the graphene, and meanwhile, the preparation process of the graphene is simple and low in manufacturing cost, so that the antistatic plastic is low in manufacturing cost and has market competitiveness.
2. PLA is a polar polymer, and hyperbranched polyethylene is a non-polar polymer, and the compatibility of the PLA and the hyperbranched polyethylene is poor, so that the hyperbranched polymer needs to be modified, and the compatibility is increased. Therefore, HBPE @ PCL is introduced, and the introduction of the PCL chain segment not only increases the compatibility of the HBPE @ PCL and the PCL chain segment, but also improves the toughness of PLA; the antistatic effect of the antistatic PLA plastic is obvious, and meanwhile, the toughness of the antistatic PLA plastic can be improved, so that the antistatic PLA plastic is wider in application range.
Drawings
FIG. 1 shows HBPE @ OH 1 H-NMR spectrum.
FIG. 2 shows HBPE @ PCL 1 H-NMR spectrum.
Fig. 3 shows the effect of the solubility of polycaprolactone group grafted hyperbranched polyethylene in different solvents: the stretching degree of the polycaprolactone group grafted hyperbranched polyethylene in chloroform and tetrahydrofuran is better than that in dichloromethane.
Figure 4 shows physical images of films prepared from three film-forming containers.
Fig. 5 shows physical diagrams of the membrane profiles of three methods of solvent removal.
Figure 6 shows a graph of the mechanical properties of two different PLA composite films.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The preparation method of the antistatic biodegradable PLA plastic of the examples of the present application is specifically described below.
Example A: polycaprolactone group grafted hyperbranched polyethylene (HBPE @ PCL)
The first step is as follows: adding 2- (trimethylsiloxy) ethyl acrylate and an anhydrous solvent A into a reaction vessel under the protection of ethylene, controlling the temperature to be 15-35 ℃, then adding a Pd-diimine catalyst dissolved in anhydrous dichloromethane, stirring and reacting for 24 hours under the conditions of the temperature of 27 ℃ and the ethylene pressure of 1atm, pouring the obtained product into acidified methanol after the polymerization is finished to terminate the polymerization, and separating and purifying the obtained polymerization reaction mixture to obtain a hyperbranched binary copolymer HBPE @ OH (nuclear magnetic characterization is shown in figure 1) containing hydroxyl end groups;
the second step is that: adding HBPE @ OH, epsilon-CL, stannous octoate and anhydrous toluene into a reaction container under the protection of nitrogen, controlling the temperature at 110 ℃ and stirring and reacting under the condition of nitrogen pressure of 1atm for 12 hours, placing the obtained product into liquid nitrogen to carry out rapid cooling after the polymerization is finished so as to terminate the polymerization, adding excessive ethanol into the product, and separating and purifying the obtained polymerization reaction mixture to obtain the hyperbranched binary copolymer HBPE @ PCL with the polycaprolactone chain segment (the nuclear magnetism is characterized as shown in figure 2).
Examples 1 to 3: effect of graphene content
1. The method for preparing the antistatic composite film by using PLA as a matrix comprises the following steps:
the first step is as follows: taking out 0.1g of dried PLA particles, and dissolving the PLA particles in 5mL of organic solvent chloroform for full dissolution to obtain a first mixture;
the second step: 80mL of chloroform was added to 320mg of HBPE @ PCL and 800mg of natural crystalline flake graphite, and the mixture was placed in an ultrasonic cell and ultrasonically dispersed at 25 ℃ and a frequency of 90Hz for 48 hours. And centrifuging for 45min at 4000r/min after the ultrasonic treatment is finished, standing for 30min, taking supernate, and performing vacuum filtration by using an organic system microporous filtering membrane with the pore diameter of 0.2 mu m to obtain the graphene dispersion liquid with stable dispersion.
The third step: the first mixture was mixed with the graphene dispersion so that the mass ratios of graphene to PLA were 0 (comparative example 1), 1 (example 1), 1. The amounts of PLA were kept consistent in examples 1-3 and comparative example 1.
The fourth step: the second mixture is stirred at a speed of 600rad/min for 30min.
The fifth step: and pouring and molding the second mixture on an ultra-flat glass sheet, and placing the ultra-flat glass sheet in a closed environment at normal temperature to remove the solvent for 8 hours to obtain the antistatic plastic.
2. The products were characterized and tested:
1) ACL 800 digital megohmmeter
The manufacturer: ACL Staticide Inc. of USA
The specific test method comprises the following steps:
the resistivity and resistance of the static dissipative surface are tested according to industry standards (e.g., ANSI/ESD test method S4).
3. Comparison and analysis of test results
Comparative example 1, example 2, and example 3 differ in the amount of graphene added to the PLA film, and three points of the film were tested, and the test results (table one) show: in the following steps of graphene: PLA =1: at 20 hours, the PBAT surface resistance is minimum, and reaches the national standard multiplied by 10 7 And (4) specifying.
Examples 4 to 6: influence of solvent
1. The method for preparing the antistatic composite film by using PLA as a matrix comprises the following steps:
the first step is as follows: 0.1g of the dried PLA particles were taken out and dissolved in 5mL of chloroform, an organic solvent, i.e., chloroform (example 4), dichloromethane (example 5), and tetrahydrofuran (example 6), respectively, to obtain a first mixture;
the second step: to 320mg of HBPE @ PCL and 800mg of natural crystalline flake graphite, 80mL of organic solvents, namely chloroform (example 4), dichloromethane (example 5) and tetrahydrofuran (example 6), were added, and the mixture was placed in an ultrasonic bath and ultrasonically dispersed at 25 ℃ and 90Hz for 48 hours. And centrifuging at 4000r/min for 45min after the ultrasonic treatment is finished, standing for 30min, taking supernatant, and performing vacuum filtration by using an organic microporous filter membrane with the pore diameter of 0.2 mu m to obtain the graphene dispersion.
The third step: the first mixture was mixed with a graphene dispersion, wherein the mass ratio of graphene to PLA particles was 1.
The fourth step: the second mixture is stirred at a speed of 600rad/min for 30min.
The fifth step: and pouring and molding the second mixture on an ultra-flat glass sheet, and placing the ultra-flat glass sheet in a closed environment at normal temperature to remove the solvent for 8 hours to obtain the antistatic plastic.
2. The products were characterized and tested:
the test method was the same as in examples 1 to 3.
3. Comparison and analysis of test results
The difference between examples 4, 5 and 6 is that the solvents used for stripping graphene and dissolving PLA are different, and the concentration of graphene in the solution after sonication is first determined, and the graphene concentration in examples 4 and 6 is the same and greater than that in example 5, for the following reasons: in the embodiment 4 and the embodiment 6, the solvents are chloroform and tetrahydrofuran, HBPE @ PCL can be well dissolved in the two solvents to assist in stripping graphene, and the Ch-pi action is generated between the HBPE @ PCL and graphite to strip the graphene, but the Ch-pi enables the HBPE @ PCL to be permanently adsorbed on the surface of the graphene, and the graphene cannot be damaged even under the action of centrifugal force and ultrasound. Therefore, the segment of hbpe @ pcl in example 4 and example 6 is relatively extended, while hbpe @ pcl in example 5 is insoluble and thus takes graphene to deposit at the bottom of the solution, so the graphene concentration in example 5 is lower. FIG. 3 shows the solubility properties of HBPE @ PCL in different solvents.
Further, when a graphene solution with the same graphene content is compounded with PLA, it is found that the antistatic performance of example 5 is inferior to that of examples 4 and 6, and the reason for this is that the solubility of the hyperbranched polyethylene in dichloromethane is inferior to that of chloroform and tetrahydrofuran, whereas in example 5, because the hyperbranched polyethylene is difficult to dissolve, even though the graphene content is the same, the amount of graphene uniformly dispersed on the surface of PLA is significantly less than that of examples 4 and 6, and thus the antistatic performance is inferior. See table two for details.
Examples 7 to 9: influence of film Forming Container
1. The method for preparing the antistatic composite film by using PLA as a matrix comprises the following steps:
the first step is as follows: taking out 0.1g of dried PLA granules, and dissolving the PLA granules in 5mL of organic solvent chloroform for full dissolution;
the second step: and (3) performing pouring molding operation, preparing polymer films by adopting different methods, placing the polymer films into super-flat glass sheets (example 7), PET (polyethylene terephthalate) films (example 8) and PTFE (polytetrafluoroethylene) molds (example 9), and removing the solvent for 8 hours at normal temperature in a closed environment to obtain the antistatic plastic.
2. The products were characterized and tested:
the test method was the same as in examples 1 to 3
3. Comparison and analysis of test results
The difference between the embodiment 7, the embodiment 8 and the embodiment 9 lies in the difference of the film forming carrier during the pouring film forming, the antistatic effect of the film formed by the three is not very different, but the film taking difficulty after the film forming is different, and the reason is that: example 8 is a film is cast on a PET film, and because PET and PLA are well compatible, taking and using are relatively difficult, and there is a risk of damaging the film; in the embodiment 8, the film is formed on the glass sheet, and the difficulty of film forming and peeling on the glass sheet is relatively simpler than that of a PET film, so that the film forming container is an ideal film forming container; in example 9, a film is cast on a PTFE plastic block, and because of the lubricity of PTFE, a PLA film can be easily formed on the surface of the PTFE plastic block and easily removed, and the PLA film has little effect on its antistatic properties, which is an ideal film-forming carrier (fig. 4), but PTFE molds have low hardness and are easily damaged by hard objects, so that the surface smoothness needs to be carefully stored.
Examples 10 to 12: influence of solvent removal method
1. The method for preparing the antistatic composite film by using PLA as a matrix comprises the following steps:
the first step is as follows: taking out the dried PLA granules, and dissolving the PLA granules in chloroform for full dissolution to obtain a first mixture;
the second step: 80mL of chloroform is added into 320mg of HBPE @ PCL and 800mg of natural crystalline flake graphite, and the mixture is placed in an ultrasonic pool and ultrasonically dispersed for 48 hours under the conditions of 25 ℃ and the frequency of 90 Hz. And centrifuging at 4000r/min for 45min after the ultrasonic treatment is finished, standing for 30min, taking supernatant, and performing vacuum filtration by using an organic microporous filter membrane with the pore diameter of 0.2 mu m to obtain the graphene dispersion liquid with stable dispersion.
The third step: the first mixture was mixed with the graphene dispersion, wherein the mass ratio of graphene to PLA particles was 1.
The fourth step: the second mixture is stirred at a speed of 600rad/min for 30min.
The fifth step: pouring and molding on an ultra-flat glass sheet, and removing the solvent in the first mixture by different methods, specifically, in example 10, blowing with cold air is used, in example 11, the solution is placed in a closed environment and the solvent is removed at normal temperature for 8h, and in example 12, the solvent is volatilized by heating to obtain the antistatic plastic.
2. The products were characterized and tested:
the test method was the same as in examples 1 to 3
3. Comparison and analysis of test results
The antistatic performance of the material is tested by casting the films in examples 10, 11 and 12 respectively, and it is found that the antistatic performance of the material is better in example 11 (see table three), and the reason why the cold air blowing solvent is used in example 10 to volatilize too fast, pores are formed inside and on the surface of the film, which affects graphene on the surface of the film to form a conductive path, and weakens the antistatic effect of the film (see fig. 5), compared with example 11, in example 12, graphene is heated and agglomerated in the heating process, and the agglomerated graphene in example 12 cannot well form a three-dimensional network structure in the polymer substrate, so that the antistatic performance of the material is poor.
Watch III
Examples 13 to 14: effect of hyperbranched Polymer species
1. The method for preparing the antistatic composite film by using PLA as a matrix comprises the following steps:
the first step is as follows: taking out the dried PLA granules, and dissolving the PLA granules in chloroform for full dissolution;
the second step is that: 80mL of chloroform is added into 320mg of HBPE @ PCL and 800mg of natural crystalline flake graphite, and the mixture is placed in an ultrasonic pool and ultrasonically dispersed for 48 hours under the conditions of 25 ℃ and the frequency of 90 Hz. And centrifuging at 4000r/min for 45min after the ultrasonic treatment is finished, taking supernatant, and performing suction filtration to obtain the graphene dispersion liquid 1 with stable dispersion.
The third step: 80mL of chloroform was added to 320mg of HBPE (prepared according to the method described in example 1 of CN 103087335A) and 800mg of natural flake graphite, and the mixture was placed in an ultrasonic cell and subjected to ultrasonic dispersion at 25 ℃ and 90Hz for 48 hours. And centrifuging at 4000r/min for 45min after the ultrasonic treatment is finished, standing for 30min, taking supernatant, and performing vacuum filtration by using an organic microporous filter membrane with the pore diameter of 0.2 mu m to obtain the graphene dispersion liquid 2 with stable dispersion.
The fourth step: the first mixture was mixed with different graphene dispersions, specifically, example 13 was graphene dispersion 1 obtained by sonicating graphite with a second step HBPE @ pcl, example 14 was graphene dispersion 2 obtained by sonicating graphite with a third step HBPE under the same conditions as the second step, wherein the mixing mass ratio of graphene to PLA particles was 1,
the fifth step: the second mixture is stirred at a speed of 600rad/min for 30min.
And a sixth step: and pouring and molding the second mixture on an ultra-flat glass sheet, and placing the ultra-flat glass sheet in a closed environment at normal temperature to remove the solvent for 8 hours to obtain the antistatic plastic.
2. The products were characterized and tested:
1) General tester 68TM series
The manufacturer: instron/Instron in America
The specific test method comprises the following steps:
the stress and strain of the plastic is tested according to industry standards such as ASTM D638-2003 test method.
3. Comparison and analysis of test results
According to the stress-strain curves of the example 13 and the example 14, the stress of the example 13 is smaller, and the elongation at break is larger (see fig. 6), and the graphene in the example 13 is prepared from hbpe @ PCL, wherein a PCL chain segment not only has better compatibility in PLA, but also provides certain flexibility for a hard chain segment of PLA, and improves the mechanical property of PLA plastic; example 14 has higher tensile stress and lower elongation at break than example 13, limiting the utility of PLA because HBPE does not provide a soft segment in the PLA matrix and does not provide better mechanical properties for PLA.
Claims (10)
1. A preparation method of a graphene composite antistatic biodegradable PLA plastic is characterized by comprising the following steps: the preparation method comprises the following steps:
1) Placing PLA granules in a blast oven for full drying, taking out the PLA granules, and dissolving the PLA granules in an organic solvent A to obtain a first mixture;
2) The Pd-diimine catalyst is used for catalyzing the copolymerization of ethylene and 2- (trimethylsiloxy) ethyl acrylate to prepare a hyperbranched binary copolymer HBPE @ OH containing hydroxyl end groups; then, taking hyperbranched binary copolymer HBPE @ OH as a macroinitiator, and initiating epoxy monomer epsilon-caprolactone to graft copolymerization through a hydroxyl end group based on a ring-opening polymerization mechanism to obtain polycaprolactone group grafted hyperbranched polyethylene HBPE @ PCL;
3) Utilizing polycaprolactone group grafted hyperbranched polyethylene HBPE @ PCL liquid phase ultrasonic stripping graphite to obtain graphene dispersion liquid;
4) Adding the graphene dispersion liquid obtained in the step 3) into the first mixture, and fully and uniformly stirring to obtain a second mixture; wherein the feeding ratio of the graphene to the PLA is 1:20-100;
5) Pouring and molding the second mixture obtained in the step 4), and removing the solvent to obtain the antistatic plastic.
2. The method of claim 1, wherein: in the step 1), the organic solvent A is one or a mixture of more of chloroform, tetrahydrofuran and dichloromethane.
3. The method of claim 1, wherein: the Pd-diimine catalyst is selected from one of the following: the acetonitrile group Pd-diimine catalyst 1 and the methyl ester group-containing six-membered ring Pd-diimine catalyst 2 have the following structural formulas:
wherein the content of the first and second substances,
4. the method of claim 1, wherein: the step 2) is specifically operated as follows: adding 2- (trimethylsiloxy) ethyl acrylate and an anhydrous solvent A into a reaction vessel under the protection of ethylene, controlling the temperature to be 15-35 ℃, then adding a Pd-diimine catalyst dissolved in the anhydrous solvent A, stirring and reacting for 12-48 hours under the conditions that the temperature is 15-35 ℃ and the ethylene pressure is 0.1-6 atm, pouring the obtained product into acidified methanol after the polymerization is finished to terminate the polymerization, and separating and purifying the obtained polymerization reaction mixture to obtain a hyperbranched binary copolymer HBPE @ OH containing hydroxyl end groups; adding hyperbranched binary copolymer HBPE @ OH, epsilon-CL, stannous octoate and anhydrous solvent B into a reaction container under the protection of nitrogen, controlling the temperature at 100-120 ℃ and the nitrogen pressure at 0.1-6 atm, stirring and reacting for 12-24 hours, placing the obtained product into liquid nitrogen for rapid cooling after the polymerization is finished to terminate the polymerization, adding excessive ethanol into the product, and separating and purifying the obtained polymerization reaction mixture to obtain polycaprolactone group grafted hyperbranched polyethylene HBPE @ PCL.
5. The method of claim 4, wherein: in the step 2), the anhydrous grade solvent A is selected from one of the following: anhydrous dichloromethane, trichloromethane or chlorobenzene; the anhydrous grade solvent B is selected from one of the following: anhydrous grade toluene, xylene or ortho-dichlorobenzene.
6. The method of claim 4, wherein: in the step 2), the mass usage amount of the Pd-diimine catalyst is 0.5-15.0 g/L (more preferably 10-15 g/L), and the mass usage amount of the 2- (trimethylsiloxy) ethyl acrylate is 0.2-1.0 mol/L (more preferably 0.4-0.6 mol/L), based on the total volume of the anhydrous grade solvent A; the mass usage of the HBPE @ OH is 10-15 g/L, the mass usage of the epsilon-caprolactone is 100-250 g/L (more preferably 150-200 g/L), and the mass usage of the stannous octoate is 1-2.5 g/L (more preferably 1.5-2.0 g/L) based on the total volume of the anhydrous solvent B.
7. The method of claim 4, wherein: in the step 2), the reaction temperature for synthesizing HBPE @ OH is 20-30 ℃, the ethylene pressure is 0.5-1.5atm, and the stirring reaction time is 20-30h; the reaction temperature for synthesizing HBPE @ PCL is 105-115 ℃, the nitrogen pressure is 0.5-1.5atm, and the stirring reaction time is 10-14h.
8. The method of claim 1, wherein: step 3) is carried out as follows: mixing graphite powder, an organic solvent B and a polycaprolactone group grafted hyperbranched binary copolymer HBPE @ PCL in proportion, wherein the organic solvent B is selected from one of the following chemical pure reagents or analytical pure reagents: tetrahydrofuran, chloroform, n-heptane, chlorobenzene, dichloromethane; and then carrying out ultrasonic treatment on the obtained mixture to obtain an initial graphene dispersion liquid, wherein the concentration of graphite powder is 0.1-1000 mg/mL, and the feeding mass ratio of HBPE @ PCL to graphite powder is 0.01-10: 1; further performing low-speed centrifugation and standing treatment to obtain a graphene dispersion liquid containing excessive HBPE @ PCL; and (3) carrying out ultra-high speed centrifugation or vacuum filtration on the obtained graphene dispersion liquid containing excessive HBPE @ PCL to remove the contained excessive HBPE @ PCL, and ultrasonically dispersing in the organic solvent B again to obtain the graphene organic dispersion liquid.
9. The method of claim 1, wherein: in the step 4), the stirring speed is controlled to be 600-800 rad/min, and the stirring time is 30-60 min.
10. The method of claim 1, wherein: and step 5), placing the second mixture obtained in the step 4) in a normal-temperature closed container, and removing the solvent at normal temperature to obtain the antistatic plastic.
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