CN114702803A - Antistatic polylactic acid material and preparation method thereof - Google Patents
Antistatic polylactic acid material and preparation method thereof Download PDFInfo
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Abstract
The application relates to the technical field of conductive composite materials, in particular to an antistatic polylactic acid material and a preparation method thereof. The application provides an antistatic polylactic acid material, including each component of following parts by weight: 80-120 parts of polylactic acid, 1-6 parts of a conductive agent, 1-5 parts of a dispersing agent and 1.7-3 parts of other auxiliary agents, wherein the conductive agent comprises carbon nano tube powder, a mixture of carbon nano tube fibers and graphene powder. The application provides an antistatic polylactic acid material uses polylactic acid as the main part, adds the conducting agent in order to improve its antistatic behavior, and wherein, the conducting agent includes the mixture of carbon nanotube powder, carbon nanotube fiber and graphite alkene powder, and its mixture distributes and can form the electrically conductive network of multidimension degree in polylactic acid, and carbon nanotube powder, carbon nanotube fiber and graphite alkene powder can improve polylactic acid material's intensity as the mixture.
Description
Technical Field
The application belongs to the technical field of conductive composite materials, and particularly relates to an antistatic polylactic acid material and a preparation method thereof.
Background
The polylactic acid is pollution-free in the production process, biodegradable, nontoxic in combustion products, safe and harmless to human bodies, environment-friendly and environment-friendly, and is an ideal green polymer material. Besides, the polylactic acid has excellent performances such as biocompatibility, glossiness, hand feeling and heat resistance, can replace non-degradable plastics such as nylon, polyethylene, polystyrene, polyvinyl chloride, ABS and the like to be used for various plastic products, food packages, snack boxes, medical supplies, non-woven fabrics and the like, is used as a packaging material, fibers, non-woven fabrics and the like, has great application space in the fields of clothing, engineering application, medical sanitation and the like, and is a material with the most development potential in the future.
Polylactic acid has high insulativity, is easy to generate static accumulation in the production and use processes, causes static dust absorption, spark discharge and the like, can cause fire, explosion, damage to packaging instruments and the like, and is not beneficial to production, processing and use. In order to solve the problem that polylactic acid is easy to generate static electricity and widen the application field of the polylactic acid, the polylactic acid needs to be subjected to antistatic treatment.
Common antistatic treatment methods are: adding ionic surfactant, non-ionic antistatic agent, high-molecular permanent antistatic agent, etc. The ionic and non-ionic antistatic agents are nondegradable, have poor thermal stability and are easy to generate polluted gas when being combusted; the addition amount of the high-molecular permanent antistatic agent is large (generally 5-20%), and the degradable performance of the polylactic acid is influenced.
In addition, in the existing antistatic polylactic acid composite material, conductive carbon black fibers and graphene are selected as conductive agents, and the volume resistivity can reach 10 to the power of 7 omega cm. The disadvantages are that: the additive type and the additive amount are too much, so that the degradability of the polylactic acid is influenced.
In the existing biodegradable antistatic polylactic acid material and the formed product thereof, the selected antistatic agent is ammonium salt, nitrate or sodium sulfate salt, and polluted gas is generated by combustion, so that the environmental protection characteristic of the polylactic acid is influenced. And the surface resistance is only 108Omega, only reach the general antistatic level.
Disclosure of Invention
The application aims to provide an antistatic polylactic acid material and a preparation method thereof, and aims to solve the problems that an existing polylactic acid plate is high in insulating property, easy to accumulate a large amount of static electricity and not beneficial to production, processing and use.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
the application provides in a first aspect an antistatic polylactic acid material, including each component of following parts by weight:
the conductive agent comprises a mixture of carbon nanotube powder, carbon nanotube fibers and graphene powder.
The application provides an antistatic polylactic acid material uses polylactic acid as the main part, adds the conducting agent in order to improve its antistatic behavior, and wherein, the conducting agent includes the mixture of carbon nanotube powder, carbon nanotube fiber and graphite alkene powder, and its mixture distributes and can form the electrically conductive network of multidimension degree in polylactic acid, and carbon nanotube powder, carbon nanotube fiber and graphite alkene powder can improve polylactic acid material's intensity as the mixture.
The antistatic polylactic acid material that this application embodiment provided because carbon nanotube powder, carbon nanotube fiber and graphite alkene powder still have excellent thermal conductivity, mechanical properties etc. add the heat resistance and the toughness that do benefit to reinforcing polylactic acid in an appropriate amount, can increase antistatic polylactic acid material's initial melting point temperature. And can improve the blackness, color smoothness and surface smoothness of the material.
The carbon nanotube powder, the carbon nanotube fiber and the graphene powder provided by the embodiment of the application are carbon materials, and do not contain pollutants such as sulfide and nitride after combustion. And because the addition amount is small, the environmental protection property and the degradable property of the polylactic acid are not influenced.
The compound ratio of antistatic polylactic acid material through control polylactic acid, conductive agent and dispersant in this application embodiment can adjust the intensity and the antistatic properties of polylactic acid material. The dispersing agent is adopted to disperse the mixture of the carbon nanotube powder, the carbon nanotube fiber and the graphene powder, so that the dispersion uniformity of the carbon nanotube powder, the carbon nanotube fiber and the graphene powder in the polylactic acid material is effectively improved, and the carbon nanotube powder, the carbon nanotube fiber and the graphene powder are facilitated to form a cross-linked structure with the polylactic acid material, so that a conductive path is formed.
The second aspect of the application provides a preparation method of an antistatic polylactic acid material, which comprises the following steps:
weighing each raw material component according to the components contained in the antistatic polylactic acid material provided by the embodiment of the application;
mixing the raw material components to obtain a mixture;
and carrying out melt mixing treatment on the mixture to obtain the antistatic polylactic acid material.
According to the preparation method of the antistatic polylactic acid material, the carbon nanotube powder, the carbon nanotube fiber, the graphene powder, the dispersing agent, the polylactic acid and other auxiliaries are mixed according to a certain proportion, and the carbon nanotube powder, the carbon nanotube fiber and the graphene powder can be dispersed in the polylactic acid main body and wrapped by the polylactic acid main body through melting and mixing treatment, so that the polylactic acid material with excellent antistatic performance and strength performance can be obtained.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, which means that there may be three relationships, for example, a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one item(s) of a, b, or c," or "at least one item(s) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the specification of the present application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms first, second, etc. are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of regulations of this application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The embodiment of the application provides an antistatic polylactic acid material, which comprises the following components in parts by weight:
the conductive agent comprises carbon nano tube powder, a mixture of carbon nano tube fibers and graphene powder.
The embodiment of the application provides antistatic polylactic acid material uses polylactic acid as the main part, and first aspect adds the conducting agent in order to improve its antistatic properties, and wherein, the conducting agent includes the mixture of carbon nanotube powder, carbon nanotube fiber and graphite alkene powder, and its mixture distributes and can form the electrically conductive network of multidimension degree in polylactic acid, and carbon nanotube powder, carbon nanotube fiber and graphite alkene powder can improve polylactic acid material's intensity as the mixture. In the second aspect, because the carbon nanotube powder, the carbon nanotube fiber and the graphene powder also have excellent heat-conducting property, mechanical property and the like, the initial melting point temperature of the antistatic polylactic acid material can be increased, and proper addition of the carbon nanotube powder, the carbon nanotube fiber and the graphene powder is beneficial to enhancing the heat resistance and toughness of the polylactic acid, and can improve the blackness, color smoothness and surface smoothness of the material. In the third aspect, the carbon nanotube powder, the carbon nanotube fiber, and the graphene powder are carbon materials, and do not contain pollutants such as sulfide and nitride after combustion. And because the addition amount is small, the environmental protection property and the degradable property of the polylactic acid are not influenced. In the fourth aspect, the compound ratio of the antistatic polylactic acid material through controlling polylactic acid, conductive agent and dispersant in the embodiment of the application can adjust the strength and antistatic property of the polylactic acid material. The polylactic acid in the above-mentioned article may be 94.5 parts, 93.1 parts, 92.1 parts, but is not limited thereto. The conductive agent may be 2 parts, 3 parts or 3.5 parts, which is beneficial to improve the conductive performance of the polylactic acid main body material, but is not limited thereto.
According to the embodiment of the application, the mixture of the carbon nanotube powder, the carbon nanotube fiber and the graphene powder is dispersed by the dispersing agent, so that the dispersion uniformity of the carbon nanotube powder, the carbon nanotube fiber and the graphene powder in the polylactic acid material is effectively improved, and the carbon nanotube powder, the carbon nanotube fiber and the graphene powder are facilitated to form a cross-linked structure with the polylactic acid material, so that a conductive path is formed. For example, the dispersant may be 1.1 parts, 1.5 parts, or 2 parts, which may be beneficial to improve the dispersion degree of the carbon nanotube powder, the carbon nanotube fiber, and the graphene powder in the polylactic acid host material, but is not limited thereto.
In some embodiments, the dispersant comprises at least one of an aqueous nonionic fatty acid derivative dispersant, a silane coupling agent. The aqueous nonionic fatty acid derivative dispersant in the above paper comprises at least one of fatty acid polyol ester and fatty acid amide, wherein the carbon chain length of the fatty acid is C6-C12. The silane coupling agent in the above publication includes at least one of KH550, KH560, KH570, and KH 792. Compared with polylactic acid materials added with ionic surfactants and nonionic antistatic agents, the dispersing agent in the paper is degradable, has good thermal stability, and is not easy to generate polluted gas during combustion. Compared with the polylactic acid material added with the macromolecular permanent antistatic agent, the additive amount is small, and the degradable performance of the polylactic acid is not influenced.
In some embodiments, in order to further improve the antistatic property and strength of the antistatic polylactic acid material, the parts by weight of the carbon nanotube powder, the carbon nanotube fiber and the graphene powder in the antistatic polylactic acid material are as follows: 0.1-4 parts of carbon nano tube powder, 1-4 parts of carbon nano tube fiber and 0.1-3 parts of graphene powder. For example, the mass ratio of the carbon nanotube powder, the carbon nanotube fiber and the graphene powder in the above text may be 2:1:1, but is not limited thereto.
In some embodiments, the carbon nanotubes in the carbon nanotube powder have a length of 5 to 20 μm and a diameter of 7 to 15nm, and the carbon nanotube fiber is prepared by drawing and twisting a carbon nanotube array. The length of the carbon nano tube fiber is 300-1000 mu m, and the diameter is 50-100 mu m; the structure of the carbon nanotube powder and the carbon nanotube fiber is further optimized, so that the dispersity of the carbon nanotube powder and the carbon nanotube fiber in polylactic acid can be improved, and excellent conductivity and strength can be endowed.
In some embodiments, the other auxiliary agents include antioxidants, and the antioxidants can improve the oxidation condition of the antistatic polylactic acid material and prolong the service life of the polylactic acid material. The antioxidant in the above context includes at least one of antioxidant 1010 and antioxidant 1076. In the embodiment of the application, the mass part of the antioxidant component in the composite material is 0.1 to 0.5 part, and the mass part of the antioxidant is 0.2 part, based on 100 parts by weight of the antistatic polylactic acid, but the invention is not limited thereto.
In some embodiments, the other auxiliary agents include a secondary antioxidant, which can act synergistically with the antioxidant to further improve the oxidation of the antistatic polylactic acid material, so as to improve the service life of the polylactic acid material. The secondary antioxidant as described above includes at least one of antioxidant 168, dilauryl thiodipropionate, distearyl thiodipropionate, and octyldiphenyl phosphite. In the embodiment of the application, the mass part of the auxiliary antioxidant component in the composite material is 0.1-0.3 part, for example, the mass part of the auxiliary antioxidant is 0.2 part, based on 100 parts of the antistatic polylactic acid, but the invention is not limited thereto.
In some embodiments, other auxiliaries include talcum powder, and the talcum powder is dispersed in the polylactic acid material, and the talcum powder in the embodiment of the application can be used as a nucleating agent to obviously improve the crystallization speed of polylactic acid, and meanwhile, the talcum powder can further improve the dispersion uniformity of carbon nanotube powder, carbon nanotube fiber and graphene powder in the melting and mixing process, and can further improve the surface smoothness of the antistatic polylactic acid material under the synergistic effect of the mixture of the carbon nanotube powder, the carbon nanotube fiber and the graphene powder. The particle size of the talcum powder is 500-10000 meshes. In the embodiment of the application, the mass part of the talc powder is 1 to 3 parts, and the mass part of the talc powder is 2 parts, for example, but not limited thereto, based on 100 parts of the antistatic polylactic acid.
In some embodiments, the antistatic polylactic acid material described herein has a surface resistance of 104Ω～105Omega. Compared with the existing polylactic acid material, the embodiment of the application provides an antistatic polylactic acid composite material modified by a carbon nanotube (carbon nanotube for short) powder/carbon nanotube fiber/graphene powder compound conductive agent, a conductive network is formed inside polylactic acid after modification treatment of the carbon nanotube (carbon nanotube for short) powder/carbon nanotube fiber/graphene powder compound conductive agent,the polylactic acid plate or granule has a surface resistance of 1013Omega is reduced to 104Ω～105Omega, can reach the antistatic level of high quality.
The antistatic polylactic acid material provided by the embodiment of the application can be prepared by the following method.
The second aspect of the embodiment of the present application provides a preparation method of an antistatic polylactic acid material, including the following steps:
s10, weighing the raw material components according to the components contained in the antistatic polylactic acid material provided by the embodiment of the application;
s20, mixing the raw material components to obtain a mixture;
and S30, carrying out melt mixing treatment on the mixture to obtain the antistatic polylactic acid material.
According to the preparation method of the antistatic polylactic acid material, the carbon nanotube powder, the carbon nanotube fiber, the graphene powder, the dispersing agent, the polylactic acid and other auxiliary agents are mixed according to a certain proportion, and the carbon nanotube powder, the carbon nanotube fiber and the graphene powder can be dispersed in the polylactic acid main body and wrapped by the polylactic acid main body through melting and mixing treatment, so that the polylactic acid material with excellent antistatic performance and strength performance can be obtained.
In the step S10, according to the formula of the antistatic polylactic acid material, the carbon nanotube powder, the carbon nanotube fiber, the graphene powder, the dispersant, the polylactic acid, and other additives are weighed according to the mass parts, the content and the preferred condition of each component are as described above, and are not described herein again for the sake of brevity.
In the step S20, the carbon nanotube powder, the carbon nanotube fiber, the graphene powder, the dispersant, the polylactic acid, and other additives are mixed, and a certain charging sequence, the number of times of mixing, and the sequence of processing may affect the dispersion degree of the components contained in the prepared antistatic polylactic acid material, and further may affect the overall performance of the prepared antistatic polylactic acid material, so that the mixing process specifically includes the following steps:
step S21: mixing carbon nanotube powder, carbon nanotube fiber and graphene powder to obtain a compound conductive agent;
step S22: mixing other auxiliary agents to obtain a fourth mixture;
step S23: and mixing the compound conductive agent, the polylactic acid, the dispersing agent and the fourth mixture to obtain a mixture.
In the first step, carbon nanotube powder, carbon nanotube fiber and graphene powder are mixed to obtain a highly dispersed compound conductive agent. And secondly, mixing other auxiliary agents to obtain a fourth highly dispersed mixture. And thirdly, mixing the compound conductive agent, the polylactic acid, the dispersing agent and the fourth mixture to obtain a highly dispersed mixture. And the three mixing processes are adopted, so that the dispersion degree of the carbon nano tube powder, the carbon nano tube fiber, the graphene powder and other auxiliary agents is favorably improved.
In step S21, in order to further uniformly mix the carbon nanotube powder, the carbon nanotube fiber, and the graphene powder, in other embodiments, the mixing process specifically includes the following steps:
1) infiltrating carbon nanotube fibers with the solution; 2) placing graphene in an aqueous solution, and performing ultrasonic treatment to form a uniformly dispersed graphene dispersion liquid; 3) adding a dispersing agent into the graphene powder dispersion liquid, adding carbon nano tube powder, continuing ultrasonic treatment, and uniformly stirring to obtain a mixed liquid; 4) dispersing the carbon nano tube fiber soaked by the solution into the mixed solution, and finally concentrating and drying to obtain the compound conductive agent. Wherein, the carbon nano tube fiber soaked by the solution adopts ethanol or polyvinyl alcohol solution; the dispersant is selected from: at least one of water, ethanol, acetone, ethyl acetate, DMF and NMP can be optimized and adjusted according to the actual dispersion and use effect. By adopting the mixing treatment mode, the dispersion uniformity of the carbon nanotube powder, the carbon nanotube fiber and the graphene powder in the compound conductive agent can be obviously improved, and the carbon nanotube fiber and the graphene powder can be more easily and uniformly dispersed in the subsequent mixing process.
In some embodiments, in order to further improve the dispersibility of the carbon nanotube powder, the carbon nanotube fiber, the graphene powder and other additives in the polylactic acid, the mixing process specifically includes the following steps:
step S24: mixing carbon nanotube powder, carbon nanotube fiber and graphene powder to obtain a compound conductive agent;
step S25: mixing polylactic acid and a dispersing agent to obtain a first mixture;
step S26: mixing other auxiliary agents to obtain a second mixture;
step S27: mixing the compound conductive agent and the first mixture to obtain a third mixture;
step S28: and mixing the second mixture and the third mixture to obtain a mixture.
According to the preparation method of the antistatic polylactic acid material, carbon nanotube powder, carbon nanotube fibers, graphene powder, a dispersing agent, polylactic acid and other auxiliaries are subjected to mixing treatment for many times.
Firstly, mixing carbon nanotube powder, carbon nanotube fiber and graphene powder to obtain a highly dispersed compound conductive agent. And secondly, mixing the polylactic acid and the dispersing agent to obtain a first mixture with high dispersion, wherein the dispersing agent is uniformly attached to the polylactic acid material. And thirdly, mixing other auxiliary agents to obtain a highly dispersed second mixture. And fourthly, mixing the highly dispersed compound conductive agent and the highly dispersed first mixture to obtain a highly dispersed third mixture, and at the moment, uniformly attaching the dispersing agent to the polylactic acid material, so that the carbon nanotube powder, the carbon nanotube fiber and the graphene powder can be prevented from agglomerating under the action of the dispersing agent, and the performance stability of the composite material is improved. And fifthly, mixing the second mixture and the third mixture which are highly dispersed to obtain a mixture which is highly dispersed as a whole. The five times of mixing process is adopted, which is beneficial to improving the dispersion degree of the carbon nano tube powder, the carbon nano tube fiber, the graphene powder and other auxiliary agents. The antistatic polylactic acid material has the advantages that the antistatic performance of the base material can be improved by the carbon nano tube powder, the carbon nano tube fiber and the graphene powder, the surface resistance of the base material is reduced, and the impact strength of the base material is increased, so that the antistatic polylactic acid material has better comprehensive performance, specifically comprises better impact strength, lower surface resistance, lower initial melting temperature and better forming performance.
In step S24, in order to further uniformly mix the carbon nanotube powder, the carbon nanotube fiber, and the graphene powder, in other embodiments, the mixing process specifically includes the following steps: in order to further uniformly mix the carbon nanotube powder, the carbon nanotube fiber and the graphene powder, the mixing treatment comprises the following steps: 1) infiltrating carbon nanotube fibers with the solution; 2) placing graphene powder in an aqueous solution, and performing ultrasonic treatment to form uniformly dispersed graphene dispersion liquid; 3) adding a dispersing agent into the graphene dispersion liquid, adding carbon nano tube powder, continuing to perform ultrasonic treatment, and uniformly stirring to obtain a mixed liquid; 4) dispersing the carbon nano tube fiber soaked by the solution into the mixed solution, and finally concentrating and drying to obtain the compound conductive agent. Wherein, the carbon nano tube fiber infiltrated by the solution adopts ethanol or polyvinyl alcohol solution; the dispersant is selected from: at least one of water, ethanol, acetone, ethyl acetate, DMF and NMP can be optimized and adjusted according to the actual dispersion use effect. By adopting the mixing treatment mode, the dispersion uniformity of the carbon nanotube powder, the carbon nanotube fiber and the graphene powder in the compound conductive agent can be obviously improved, and the carbon nanotube fiber and the graphene powder can be more easily and uniformly dispersed in the subsequent mixing process.
In some embodiments, the carbon nanotube powder, the carbon nanotube fibers and the graphene powder are pre-dispersed by mechanical mixing and homogeneous dispersion to obtain the compound conductive agent. The carbon nano tube powder, the carbon nano tube fiber and the graphene powder are pre-dispersed by the method, so that the agglomeration action force of the carbon nano tube, such as van der Waals force, can be effectively destroyed, and the interior of the compound conductive agent is uniformly dispersed.
In some embodiments, the polylactic acid and the dispersant are pre-dispersed by mechanical mixing and homogeneous dispersion to obtain a first blend. By the method, the dispersing agent and the polylactic acid are pre-dispersed, so that the dispersing agent can be uniformly dispersed in the polylactic acid main body, and a favorable basis is provided for subsequent dispersion. The equipment for implementing the mechanical mixing and homogeneous dispersion comprises a high-speed mixer, and the mixing time is 2-6 min.
In some embodiments, the other adjuvants are pre-dispersed by mechanical mixing and homogeneous dispersion to give a first blended material. The method is used for pre-dispersing other additives, so that the agglomeration acting force of the other additives, such as Van der Waals force, can be effectively destroyed, and the other additives are uniformly dispersed. The equipment for implementing the mechanical mixing and homogeneous dispersion comprises a high-speed mixer, and the mixing time is 2-6 min.
In some embodiments, the compounded conductive agent and the first mixed material are pre-dispersed by mechanical mixing and homogeneous dispersion to obtain a third mixed material. By the method, the compound conductive agent and the first mixture are dispersed, and the dispersing agent is uniformly attached to the polylactic acid material, so that the condition that carbon nanotube powder, carbon nanotube fiber and graphene powder are agglomerated can be avoided, and a favorable basis is provided for subsequent dispersion. The equipment for implementing the mechanical mixing and homogeneous dispersion comprises a high-speed mixer, and the mixing time is 5-10 min.
In some embodiments, the second and third mixes are pre-dispersed by mechanical mixing and homogeneous dispersion, providing an advantageous basis for subsequent melt processing, as a highly dispersed mixture as a whole. The equipment for implementing the mechanical mixing and homogeneous dispersion comprises a high-speed mixer, and the mixing time is 5-10 min.
In step S30, the apparatus for performing the melt kneading process is a twin-screw extrusion apparatus.
In some embodiments, the twin screw extrusion process has a processing screw temperature of 150-230 ℃ at which the polylactic acid material is completely melted to obtain a resin melt. Specifically, the temperature of the feeding area is 150-200 ℃, the temperature of the plasticizing area is 180-230 ℃, and the extrusion temperature of the die head is 180-230 ℃. The melting temperature is 230-250 ℃, the rotating speed of the screw is 200-470 r/min, the rotating speed of the main machine is 5-15 HZ, and the vacuum degree is 0.08-0.09 MPa. After the resin is melted, the carbon nanotube powder, the carbon nanotube fiber and the graphene powder are uniformly dispersed in the melted resin due to the uniformity of the overall dispersion of the mixture. The parameter setting of the extrusion process is a parameter range with good dispersion effect of each component obtained based on a large number of theories and practices based on the characteristics of the raw materials, but is not limited to the parameter range.
In order to make the above implementation details and operations of the present application clearly understood by those skilled in the art and to make the advanced performance of the antistatic polylactic acid material and the preparation method of the present application example obviously appear, the above technical solution is illustrated by a plurality of examples below.
Example 1
The first aspect of this embodiment provides an antistatic polylactic acid material, which is composed of the following components in parts by weight: 94.5 parts of polylactic acid, 2 parts of conductive agent carbon nano tube powder/carbon nano tube fiber/graphene powder (the ratio of the three is 2:1:1), 1.1 parts of dispersant fatty acid polyol ester, 10100.2 parts of antioxidant, 1680.2 parts of antioxidant and 2 parts of talcum powder (10000 meshes).
In a second aspect of this embodiment, a method for preparing an antistatic polylactic acid material is provided, including the following steps:
step S10: the components are weighed according to the formula of 94.5 parts of polylactic acid, 2 parts of conductive agent carbon nano tube powder/carbon nano tube fiber/graphene powder (the ratio of the three is 2:1:1), 1.1 parts of dispersant fatty acid polyol ester, 10100.2 parts of antioxidant, 1680.2 parts of antioxidant and 2 parts of talcum powder (10000 meshes).
Step S24: the step of mixing the carbon nanotube powder, the carbon nanotube fiber and the graphene powder specifically comprises the following steps: 1) soaking carbon nanotube fiber with polyvinyl alcohol solution; 2) placing graphene in an aqueous solution, and performing ultrasonic treatment to form a uniformly dispersed graphene dispersion liquid; 3) adding a dispersing agent acetone into the graphene dispersion liquid, adding carbon nano tube powder, continuing to perform ultrasonic treatment, and uniformly stirring to obtain a mixed solution; 4) dispersing the infiltrated carbon nanotube fiber in the mixed solution, and finally concentrating and drying to obtain the compound conductive agent.
Step S25: firstly, putting polylactic acid and dispersant fatty acid polyol ester into a high-speed mixer to be fully mixed for 4min to obtain a first mixture;
step S26: placing the antioxidant 1010, the antioxidant 168 and the talcum powder into a high-speed mixer to be fully mixed for 3min to obtain a second mixture;
step S27: putting the compound conductive agent and the first mixture into a high-speed mixer to be fully mixed for 3min to obtain a third mixture;
step S28: putting the second mixture and the third mixture into a high-speed mixer, and fully mixing for 5min to obtain a mixture;
step S30: and adding the mixed raw materials into a double-screw extruder for granulation to obtain the carbon nano tube modified antistatic polylactic acid granules. Wherein the temperature of the processing screw is 180-200 ℃, the temperature of the feeding area is 160-180 ℃, the temperature of the plasticizing area is 200-210 ℃, and the extrusion temperature of the die head is 210 ℃. The rotating speed of the screw is 250r/min, the rotating speed of the main machine is 5HZ, and the vacuum degree is 0.08-0.09 MPa.
Example 2
The first aspect of this embodiment provides an antistatic polylactic acid material, which is composed of the following components in parts by weight: 93.1 parts of polylactic acid, 3 parts of conductive agent carbon nano tube powder/carbon nano tube fiber/graphene powder (the ratio of the three is 2:1:1), 1.5 parts of dispersant fatty acid amide, 10760.2 parts of antioxidant, 1680.2 parts of antioxidant and 2 parts of talcum powder (5000 meshes).
In a second aspect of this embodiment, a method for preparing an antistatic polylactic acid material is provided, including the following steps:
step S10: the components are weighed according to the formula of 93.1 parts of polylactic acid, 3 parts of conductive agent carbon nano tube powder/carbon nano tube fiber/graphene powder (the ratio of the three is 2:1:1), 1.5 parts of dispersant fatty acid amide, 10760.2 parts of antioxidant, 1680.2 parts of antioxidant and 2 parts of talcum powder (5000 meshes).
Step S24: the step of mixing the carbon nanotube powder, the carbon nanotube fiber and the graphene powder comprises the following steps: 1) soaking carbon nanotube fibers in an ethanol solution; 2) placing graphene in an aqueous solution, and performing ultrasonic treatment to form a uniformly dispersed graphene dispersion liquid; 3) adding a dispersant ethyl acetate into the graphene dispersion liquid, adding carbon nano tube powder, continuing ultrasonic treatment, and uniformly stirring to obtain a mixed solution; 4) dispersing the infiltrated carbon nanotube fiber in the mixed solution, and finally concentrating and drying to obtain the compound conductive agent.
Step S25: firstly, putting polylactic acid and fatty acid amide as a dispersant into a high-speed mixer to be fully mixed for 4min to obtain a first mixture;
step S26: putting the antioxidant 1076, the antioxidant 168 and the talcum powder into a high-speed mixer, and fully mixing for 3min to obtain a second mixture;
step S27: putting the compound conductive agent and the first mixture into a high-speed mixer to be fully mixed for 3min to obtain a third mixture;
step S28: putting the second mixture and the third mixture into a high-speed mixer, and fully mixing for 5min to obtain a mixture;
step S30: and adding the mixed raw materials into a double-screw extruder for granulation to obtain the carbon nano tube modified antistatic polylactic acid granules. Wherein the processing screw temperature is 200-210 ℃, the feeding zone temperature is 160-180 ℃, the plasticizing zone temperature is 200-210 ℃, and the die head extrusion temperature is 210 ℃. The rotating speed of the screw is 250r/min, the rotating speed of the main machine is 5HZ, and the vacuum degree is 0.08-0.09 MPa.
Example 3
The embodiment provides an antistatic polylactic acid material in a first aspect, which comprises the following components in parts by weight:
92.1 parts of polylactic acid, 3.5 parts of conductive agent carbon nano tube powder/carbon nano tube fiber/graphene powder (the ratio of the three is 2:1:1), 2 parts of dispersant fatty acid polyol ester, 10100.2 parts of antioxidant, 1680.2 parts of antioxidant and 2 parts of talcum powder (5000 meshes).
In a second aspect of this embodiment, a method for preparing an antistatic polylactic acid material is provided, including the following steps:
step S10: weighing the components according to a formula of 92.1 parts of polylactic acid, 3.5 parts of conductive agent carbon nano tube powder/carbon nano tube fiber/graphene powder (the ratio of the three is 2:1:1), 2 parts of dispersant fatty acid polyol ester, 10100.2 parts of antioxidant, 1680.2 parts of antioxidant and 2 parts of talcum powder (5000 meshes).
Step S24: the step of mixing the carbon nanotube powder, the carbon nanotube fiber and the graphene powder specifically comprises the following steps: 1) soaking carbon nanotube fiber with polyvinyl alcohol solution; 2) placing graphene in an aqueous solution, and performing ultrasonic treatment to form a uniformly dispersed graphene dispersion liquid; 3) adding a dispersant ethanol into the graphene dispersion liquid, adding carbon nanotube powder, continuing to perform ultrasonic treatment, and stirring uniformly to obtain a mixed solution; 4) dispersing the infiltrated carbon nanotube fiber in the mixed solution, and finally concentrating and drying to obtain the compound conductive agent.
Step S25: firstly, putting polylactic acid and dispersant fatty acid polyol ester into a high-speed mixer to be fully mixed for 4min to obtain a first mixture;
step S26: placing the antioxidant 1010, the antioxidant 168 and the talcum powder into a high-speed mixer to be fully mixed for 3min to obtain a second mixture;
step S27: putting the compound conductive agent and the first mixture into a high-speed mixer to be fully mixed for 3min to obtain a third mixture;
step S28: putting the second mixture and the third mixture into a high-speed mixer, and fully mixing for 5min to obtain a mixture;
step S30: and adding the mixed raw materials into a double-screw extruder for granulation to obtain the carbon nano tube modified antistatic polylactic acid granules. Wherein the processing screw temperature is 200-210 ℃, the feeding zone temperature is 160-180 ℃, the plasticizing zone temperature is 200-210 ℃, and the die head extrusion temperature is 210 ℃. The rotating speed of the screw is 250r/min, the rotating speed of the main machine is 5HZ, and the vacuum degree is 0.08-0.09 MPa.
Comparative example 1
A conventional polylactic acid material is provided in this comparative example, which is commercially available.
Comparative example 2
Compared with the embodiment 1, the comparative example is different in that the conductive agent is formed by compounding (1: 1) carbon nano tube powder and graphene powder; the other operations are exactly the same.
Performance test
The antistatic polylactic acid materials in examples 1 to 3 and comparative examples 1 and 2 were subjected to performance tests, and the test results are shown in table 1.
TABLE 1
| Numbering | Impact strength KJ/m2 | Surface resistance omega | Initial melting Point |
| Example 1-2% conductive agent | 3.2 | Power of 10 to the 6.9 th power | 162℃ |
| Example 2-3% conductive agent | 3.6 | Power of 10 to the 5.0 power | 165.5℃ |
| Example 3-3.5% conductive agent | 3.5 | Power of 4.5 of 10 | 165.3℃ |
| Comparative example 1 pure PLA | 2.9 | Power of 13.5 of 10 | 160℃ |
| Comparative example 2 | 3.1 | Power of 8.0 of 10 | 161℃ |
As can be seen from table 1, from examples 1 to 3, the mass ratio of the mixture of polylactic acid and carbon nanotube powder, carbon nanotube fiber and graphene powder was 94.5: 2. 93.1: 3. 92.1: 3.5, the three key indexes of the antistatic polylactic acid material obtained by the method are obviously improved, and specifically, compared with the comparative example 1, the impact strength of the antistatic polylactic acid material provided by the examples 1 to 3 is increased, and the surface resistance and the initial melting point are improved. Among them, the overall performance and cost efficiency of example 2 (the mass ratio of the mixture of polylactic acid and carbon nanotube powder, carbon nanotube fiber and graphene powder is 93.1: 3) are the highest. The conductive agent adopted in the comparative example 2 is formed by compounding carbon nanotube powder and graphene powder (1: 1), and the surface resistance of the prepared antistatic polylactic acid is increased, possibly because the integrity of a conductive network is reduced due to the lack of carbon nanotube fibers.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The antistatic polylactic acid material is characterized by comprising the following components in parts by weight:
the conductive agent comprises carbon nano tube powder, a mixture of carbon nano tube fibers and graphene powder.
2. The antistatic polylactic acid material of claim 1, wherein the carbon nanotube powder, the carbon nanotube fiber and the graphene powder are in the following parts by weight:
0.1 to 4 parts of carbon nanotube powder
1-4 parts of carbon nanotube fiber
0.1-3 parts of graphene powder;
or/and the length of the carbon nano tube in the carbon nano tube powder is 5-20 mu m, and the tube diameter is 7-15 nm;
or/and the length of the carbon nano tube fiber is 300-1000 mu m, and the diameter is 50-100 mu m.
3. The antistatic polylactic acid material as claimed in claim 1 or 2, wherein the dispersant comprises at least one of an aqueous nonionic fatty acid derivative dispersant and a silane coupling agent;
and/or the other auxiliary agent comprises at least one of an antioxidant, an auxiliary antioxidant and talcum powder.
4. The antistatic polylactic acid material according to claim 3, wherein the aqueous nonionic fatty acid derivative dispersant comprises at least one of a fatty acid polyol ester, a fatty acid amide;
or/and the silane coupling agent comprises at least one of KH550, KH560, KH570 and KH 792;
or/and the antioxidant comprises at least one of antioxidant 1010 and antioxidant 1076;
or/and the auxiliary antioxidant comprises at least one of antioxidant 168, dilauryl thiodipropionate, stearyl thiodipropionate and diphenyl octylphosphite;
and/or the particle size of the talcum powder is 500-10000 meshes.
5. The antistatic polylactic acid material according to any one of claims 1, 2 and 4, wherein the surface resistance of the antistatic polylactic acid material is 104Ω～105Ω。
6. The preparation method of the antistatic polylactic acid material is characterized by comprising the following steps:
weighing the raw material components according to the components contained in the antistatic polylactic acid material of any one of claims 1 to 5;
mixing the raw material components to obtain a mixture;
and carrying out melt mixing treatment on the mixture to obtain the antistatic polylactic acid material.
7. The method for preparing the antistatic polylactic acid material of claim 6, wherein the mixing treatment specifically comprises the following steps:
mixing carbon nanotube powder, carbon nanotube fiber and graphene powder to obtain a compound conductive agent;
mixing polylactic acid and a dispersing agent to obtain a first mixture;
mixing other auxiliary agents to obtain a second mixture;
mixing the compound conductive agent and the first mixture to obtain a third mixture;
mixing the second mixture and the third mixture to obtain a mixture;
or
Mixing carbon nanotube powder, carbon nanotube fiber and graphene powder to obtain a compound conductive agent;
mixing other auxiliary agents to obtain a fourth mixture;
and mixing the compound conductive agent, the polylactic acid, the dispersing agent and the fourth mixture to obtain the mixture.
8. The method for preparing the antistatic polylactic acid material according to claim 6, wherein the melt-kneading treatment is a twin-screw extrusion treatment.
9. The method for preparing the antistatic polylactic acid material according to claim 8, wherein in the double-screw extrusion treatment, the processing screw temperature is 150-230 ℃, the screw rotation speed is 200-470 r/min, the host rotation speed is 5-15 HZ, and the vacuum degree is 0.08-0.09 MPa.
10. The method for preparing the antistatic polylactic acid material according to claim 9, wherein the temperature of the feeding zone is 150 to 200 ℃, the temperature of the plasticizing zone is 180 to 230 ℃, and the extrusion temperature of the die head is 180 to 230 ℃.
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