CN114702803B - 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 which comprises the following components in parts by weight: 80-120 parts of polylactic acid, 1-6 parts of conductive agent, 1-5 parts of dispersing agent and 1.7-3 parts of other auxiliary agents, wherein the conductive agent comprises a mixture of carbon nano tube powder, carbon nano tube fiber and graphene powder. The antistatic polylactic acid material provided by the application takes polylactic acid as a main body, and the conductive agent is added to improve the antistatic performance of the polylactic acid material, wherein the conductive agent comprises a mixture of carbon nano tube powder, carbon nano tube fiber and graphene powder, the mixture is distributed in the polylactic acid to form a multi-dimensional conductive network, and the strength of the polylactic acid material can be improved by taking the mixture of the carbon nano tube powder, the carbon nano tube fiber and the graphene powder.
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 production process has no pollution, is biodegradable, has no toxicity of combustion products, is safe and harmless to human bodies, is environment-friendly and environment-friendly, and is an ideal green high polymer material. Besides, the polylactic acid has excellent performances of biocompatibility, glossiness, good hand feeling, heat resistance and the like, can replace non-degradable plastics such as nylon, polyethylene, polystyrene, polyvinyl chloride, ABS and the like to be used for various plastic products, food packaging, snack boxes, medical supplies, non-woven fabrics and the like, is used as packaging materials, 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 the material with the most development potential in the future.
Polylactic acid has high insulativity, is easy to generate static electricity accumulation in the production and use processes, causes static dust collection, spark discharge and the like, can cause fire, explosion, damage to packaging instruments and the like, and is unfavorable for production, processing and use. In order to solve the problem that polylactic acid is easy to generate static electricity and widen the application field, antistatic treatment is needed to be carried out on the polylactic acid.
The common antistatic treatment methods are: adding ionic surfactant, nonionic antistatic agent, and polymer permanent antistatic agent. The ionic and nonionic antistatic agents are nondegradable in components, poor in thermal stability and easy to produce polluted gas after combustion; the polymer permanent antistatic agent has large addition amount (generally 5% -20%) and affects the degradability of polylactic acid.
In addition, the existing antistatic polylactic acid composite material adopts conductive carbon black fibers and graphene as conductive agents, and the volume resistivity can be 10 to the power of Ω & cm. Disadvantages: the variety and the amount of the auxiliary agents are too large, which affects the degradability of the polylactic acid.
The existing biodegradable antistatic polylactic acid material and its molded product adopts ammonium salt, nitrate or sodium sulfate salt as antistatic agent, and has pollution gas in burning, affecting the environment protection property of polylactic acid. And the surface resistance is only 10 8 Omega, only a general antistatic level can be reached.
Disclosure of Invention
Aiming at the prior art, the application aims to provide an antistatic polylactic acid material and a preparation method thereof, and aims to solve the problems that the existing polylactic acid plate has high insulativity, is easy to accumulate a large amount of static electricity and is unfavorable for production, processing and use.
In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:
the application provides an antistatic polylactic acid material, which comprises the following components in parts by weight:
the conductive agent comprises a mixture of carbon nanotube powder, carbon nanotube fiber and graphene powder.
The antistatic polylactic acid material provided by the application takes polylactic acid as a main body, and the conductive agent is added to improve the antistatic performance of the polylactic acid material, wherein the conductive agent comprises a mixture of carbon nano tube powder, carbon nano tube fiber and graphene powder, the mixture is distributed in the polylactic acid to form a multi-dimensional conductive network, and the strength of the polylactic acid material can be improved by taking the mixture of the carbon nano tube powder, the carbon nano tube fiber and the graphene powder.
According to the antistatic polylactic acid material provided by the embodiment of the application, the carbon nano tube powder, the carbon nano tube fiber and the graphene powder also have excellent heat conduction performance, mechanical property and the like, and the proper amount of the antistatic polylactic acid material is added to be beneficial to enhancing the heat resistance and toughness of the polylactic acid, so that the initial melting point temperature of the antistatic polylactic acid material can be increased. And can improve the blackness, the color finish and the 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, nitride and the like after combustion. And the addition amount is small, so that the environmental protection and the degradation property of the polylactic acid are not affected.
According to the embodiment of the application, the strength and antistatic performance of the polylactic acid material can be adjusted by controlling the compounding ratio of the polylactic acid, the conductive agent and the dispersing agent. According to the application, 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 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, comprising the following steps:
according to the components contained in the antistatic polylactic acid material provided by the embodiment of the application, weighing all raw material components;
mixing the raw material components to obtain a mixture;
and (3) 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 nano tube powder, the carbon nano tube fiber, the graphene powder, the dispersing agent, the polylactic acid and other auxiliary agents are mixed according to a certain proportion, and after melt mixing treatment, the carbon nano tube powder, the carbon nano tube fiber and the graphene powder can be dispersed in the polylactic acid main body and are wrapped by the polylactic acid main body, 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 schemes and beneficial effects to be solved more clear, the application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
In the present application, the term "and/or" describes an association relationship of an association object, which means that three relationships may exist, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (a), b, or c)", or "at least one (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, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process does not mean that the sequence of execution is sequential, and some or all of the steps may be executed in parallel or sequentially, where the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the present specification 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 weights of the relevant components mentioned in the description of the embodiments of the present application may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present application are scaled up or down within the scope of the disclosure of the embodiments of the present application. Specifically, the mass described in the specification of the embodiment of the application can be mass units known in the chemical industry field such as mu g, mg, g, kg.
The terms first and second are used for descriptive purposes only and are not to be construed as indicating or implying any relative importance or number of features indicated in order to distinguish one object from another. 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 the inventive embodiments. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such 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 a mixture of carbon nanotube powder, carbon nanotube fiber and graphene powder.
The embodiment of the application provides an antistatic polylactic acid material which takes polylactic acid as a main body, and a conductive agent is added to improve the antistatic property of the material, wherein the conductive agent comprises a mixture of carbon nano tube powder, carbon nano tube fiber and graphene powder, the mixture is distributed in the polylactic acid to form a multi-dimensional conductive network, and the strength of the polylactic acid material can be improved by taking the mixture of the carbon nano tube powder, the carbon nano tube fiber and the graphene powder. In the second aspect, since 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 the appropriate amount of the antistatic polylactic acid material is added to be beneficial to enhancing the heat resistance and toughness of the polylactic acid, and the blackness, the color finish and the surface smoothness of the material can be improved. 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 the addition amount is small, so that the environmental protection and the degradation property of the polylactic acid are not affected. In the fourth aspect, the antistatic polylactic acid material in the embodiment of the application can adjust the strength and antistatic performance of the polylactic acid material by controlling the compounding ratio of the polylactic acid, the conductive agent and the dispersing agent. The polylactic acid 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 may be advantageous for improving the conductive properties of the polylactic acid host 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 form a cross-linked structure with the polylactic acid material, so that a conductive path is formed. For example, the dispersing agent may be 1.1 part, 1.5 parts, or 2 parts, which may be advantageous for improving the dispersibility 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 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 text includes at least one of KH550, KH560, KH570, KH 792. Compared with polylactic acid materials added with ionic surfactants and nonionic antistatic agents, the dispersing agent is degradable, has good thermal stability and is not easy to generate pollution gas after combustion. Compared with polylactic acid materials added with macromolecule permanent antistatic agents, the polylactic acid material has small addition amount and does not influence the degradability of polylactic acid.
In some embodiments, in order to further improve the antistatic property and strength of the antistatic polylactic acid material, the weight parts of the carbon nanotube powder, the carbon nanotube fiber and the graphene powder in the antistatic polylactic acid material are as follows: 0.1 to 4 parts of carbon nano tube powder, 1 to 4 parts of carbon nano tube fiber and 0.1 to 3 parts of graphene powder. For example, the mass ratio of the carbon nanotube powder, the carbon nanotube fiber and the graphene powder may be 2:1:1, but is not limited thereto.
In some embodiments, the carbon nanotube length of the carbon nanotube powder is 5-20 μm, the tube diameter is 7-15 nm, 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 nano tube powder and the carbon nano tube fiber is further optimized, so that the dispersity of the carbon nano tube powder and the carbon nano tube fiber in the polylactic acid can be improved, and excellent conductivity and strength can be endowed.
In some embodiments, the other additives include antioxidants that improve the oxidation of the antistatic polylactic acid material and increase the useful life of the polylactic acid material. The antioxidant comprises at least one of antioxidant 1010 and antioxidant 1076. In the embodiment of the application, the weight part of the antioxidant component in the composite material is 0.1-0.5 part, and the weight part of the antioxidant is 0.2 part, based on 100 parts of the antistatic polylactic acid, for example, but not limited thereto.
In some embodiments, other additives include auxiliary antioxidants that can act synergistically with the antioxidants to further improve the oxidation of the antistatic polylactic acid material to increase the useful life of the polylactic acid material. The auxiliary antioxidant comprises at least one of antioxidant 168, dilauryl thiodipropionate, dioctadecyl thiodipropionate and diphenyl octyl phosphite. In the embodiment of the application, based on 100 parts by weight of antistatic polylactic acid, the weight part of the auxiliary antioxidant component in the composite material is 0.1-0.3 part, and the weight part of the auxiliary antioxidant is 0.2 part by way of example, but is not limited to the above.
In some embodiments, other auxiliary agents include talcum powder, wherein talcum powder is dispersed in the polylactic acid material, and the talcum powder can be used as a nucleating agent to obviously improve the crystallization speed of the polylactic acid, and meanwhile, the talcum powder can further improve the dispersion uniformity of carbon nano tube powder, carbon nano tube fiber and graphene powder in the melting and mixing process, and can cooperate with the mixture of the carbon nano tube powder, the carbon nano tube fiber and the graphene powder to further improve the surface smoothness of the antistatic polylactic acid material. The particle size of the talcum powder is 500-10000 meshes. In the embodiment of the application, the weight part of talcum powder is 1-3 parts based on 100 parts of antistatic polylactic acid, and the weight part of talcum powder is 2 parts by way of example and not limitation.
In some embodiments, the antistatic polylactic acid material described above has a surface resistance of 10 4 Ω～10 5 Omega. Compared with the existing polylactic acid material, the embodiment of the application provides an antistatic polylactic acid composite material modified by carbon nano tube (carbon nano tube) powder/carbon nano tube fiber/graphene powder compound conductive agent, after modification treatment of the carbon nano tube (carbon nano tube) powder/carbon nano tube fiber/graphene powder compound conductive agent, a conductive network is formed inside polylactic acid, and the surface resistance of a polylactic acid plate or granule is 10 13 Omega decrease to 10 4 Ω～10 5 Omega, can reach high-quality antistatic level.
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 application provides a preparation method of an antistatic polylactic acid material, which comprises the following steps:
s10, weighing all 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, provided by the embodiment of the application, the carbon nano tube powder, the carbon nano tube fiber, the graphene powder, the dispersing agent, the polylactic acid and other auxiliary agents are mixed according to a certain proportion, and the carbon nano tube powder, the carbon nano tube fiber and the graphene powder can be dispersed in the polylactic acid main body and are wrapped by the polylactic acid main body through melt 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 formulation 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 in the corresponding parts by weight, and the contents and the preferred conditions of the components are as described above, so that the description is omitted here for saving the space.
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 feeding sequence, the number of times of mixing treatment and the sequence of treatment affect the dispersion degree of the components contained in the prepared antistatic polylactic acid material, and further affect the overall performance of the prepared antistatic polylactic acid material, so the mixing treatment 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, polylactic acid, the dispersing agent and the fourth mixture to obtain a mixture.
In the first step, the embodiment of the application carries out mixing treatment on the carbon nano tube powder, the carbon nano tube fiber and the graphene powder to obtain the highly dispersed compound conductive agent. And secondly, mixing other auxiliary agents to obtain a highly dispersed fourth mixture. Thirdly, mixing the compound conductive agent, polylactic acid, the dispersing agent and the fourth mixture to obtain a highly dispersed mixture. The three mixing processes are adopted, so that the dispersity of the carbon nano tube powder, the carbon nano tube fiber, the graphene powder and other auxiliary agents is improved.
In the step S21, in order to further mix the carbon nanotube powder, the carbon nanotube fiber and the graphene powder uniformly, in other embodiments, the mixing process specifically includes the following steps:
1) Soaking the carbon nano tube fiber in the solution; 2) Placing graphene in an aqueous solution, and performing ultrasonic treatment to form uniformly dispersed graphene dispersion liquid; 3) Adding a dispersing agent into the graphene powder dispersion liquid, adding carbon nano tube powder, continuing to carry out ultrasonic treatment, and uniformly stirring to obtain a mixed liquid; 4) Dispersing the carbon nanotube fiber infiltrated by the solution into the mixed solution, and finally concentrating and drying to obtain the compound conductive agent. Wherein, the solution is used for infiltrating the carbon nano tube fiber by adopting 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 using effect. By 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 powder, the carbon nanotube fiber and the graphene powder are easier to uniformly disperse in the subsequent mixing process.
In some embodiments, in order to further improve the dispersity of the carbon nanotube powder, the carbon nanotube fiber, the graphene powder and other additives in the polylactic acid, the mixing treatment 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 with 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, provided by the embodiment of the application, the carbon nano tube powder, the carbon nano tube fiber, the graphene powder, the dispersing agent, the polylactic acid and other auxiliary agents are subjected to multiple mixing treatment.
The first step, mixing the carbon nanotube powder, the carbon nanotube fiber and the graphene powder to obtain the highly dispersed compound conductive agent. And secondly, firstly mixing the polylactic acid and the dispersing agent to obtain a first highly dispersed mixture, wherein the dispersing agent is uniformly adhered 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, wherein the dispersing agent is uniformly attached to the polylactic acid material at the moment, and the agglomeration of the carbon nano tube powder, the carbon nano tube fiber and the graphene powder can be avoided under the action of the dispersing agent, so that the performance stability of the composite conductive agent is improved. And fifthly, mixing the second mixture and the third mixture which are highly dispersed to obtain an overall highly dispersed mixture. The adoption of the five-time mixing process is beneficial to improving the dispersity of the carbon nano tube powder, the carbon nano tube fiber, the graphene powder and other auxiliary agents. The carbon nano tube powder, the carbon nano tube fiber and the graphene powder can improve the antistatic performance of the matrix material, reduce the surface resistance of the matrix material and increase the impact strength of the matrix material, so that the antistatic polylactic acid material has better comprehensive performance, and specifically comprises better impact strength, lower surface resistance, lower initial melting temperature and better forming performance.
In the step S24, in order to further mix the carbon nanotube powder, the carbon nanotube fiber and the graphene powder uniformly, 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) Soaking the carbon nano tube fiber in the solution; 2) Placing graphene powder in an aqueous solution, and performing ultrasonic treatment to form uniformly dispersed graphene dispersion; 3) Adding a dispersing agent into the graphene dispersion liquid, adding carbon nano tube powder, continuing to carry out ultrasonic treatment, and uniformly stirring to obtain a mixed liquid; 4) Dispersing the carbon nanotube fiber infiltrated by the solution into the mixed solution, and finally concentrating and drying to obtain the compound conductive agent. Wherein, the solution is used for infiltrating the carbon nano tube fiber by adopting 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 using effect. By 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 powder, the carbon nanotube fiber and the graphene powder are easier to uniformly disperse in the subsequent mixing process.
In some embodiments, the carbon nanotube powder, the carbon nanotube fiber, and the graphene powder are pre-dispersed by mechanical mixing and homogeneous dispersion to obtain the compound conductive agent. By the method, the carbon nanotube powder, the carbon nanotube fiber and the graphene powder are pre-dispersed, so that the agglomeration acting force of the carbon nanotubes, such as Van der Waals force, can be effectively destroyed, and the inside of the compound conductive agent is uniformly dispersed.
In some embodiments, the polylactic acid and the dispersant are pre-dispersed by mechanical mixing and homogenous dispersion to provide a first blend. The dispersing agent and the polylactic acid are pre-dispersed by the method, 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 carrying out the mechanical mixing and the 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 homogenous dispersion to obtain the first mix. By the aid of the method, the other auxiliary agents are pre-dispersed, so that the agglomeration acting force of the other auxiliary agents, such as Van der Waals force, can be effectively destroyed, and the other auxiliary agents are uniformly dispersed inside. The equipment for carrying out the mechanical mixing and the 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 mixture are pre-dispersed by mechanical mixing and homogeneous dispersion to obtain a third mixture. The method is used for carrying out dispersion treatment on the compound conductive agent and the first mixture, and the dispersing agent is uniformly attached to the polylactic acid material, so that the condition that carbon nano tube powder, carbon nano tube fiber and graphene powder are agglomerated can be avoided, and a favorable foundation is provided for subsequent dispersion. The equipment for carrying out the mechanical mixing and the homogeneous dispersion comprises a high-speed mixer, and the mixing time is 5-10 min.
In some embodiments, the second and third mixtures are pre-dispersed by mechanical mixing and homogeneous dispersion, the overall highly dispersed mixture providing an advantageous basis for subsequent melt processing. The equipment for carrying out the mechanical mixing and the homogeneous dispersion comprises a high-speed mixer, and the mixing time is 5-10 min.
In the above step S30, the apparatus for performing the melt kneading process is a twin screw extrusion apparatus.
In some embodiments, in the twin screw extrusion process, the processing screw temperature is 150-230 ℃, at which the polylactic acid material is completely melted, resulting in 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 screw rotating speed is 200-470 r/min, the host rotating speed 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 dispersing effect of each component based on a large number of theories and practice summary aiming at the characteristics of raw materials, but is not limited to the above.
In order that the above implementation details and operation of the present application may be clearly understood by those skilled in the art, and that the improved performance of the antistatic polylactic acid material and the preparation method according to the embodiments of the present application may be significantly embodied, the above technical solutions are exemplified by the following examples.
Example 1
The first aspect of the embodiment provides an antistatic polylactic acid material, which comprises 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, 0.2 part of antioxidant 1010, 0.2 part of antioxidant 168 and 2 parts of talcum powder (10000 meshes).
The second aspect of the present embodiment provides a method for preparing an antistatic polylactic acid material, including the steps of:
step S10: 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, 0.2 part of antioxidant 1010, 0.2 part of antioxidant 168, 2 parts of talcum powder (10000 meshes), and weighing all the components.
Step S24: the step of mixing the carbon nanotube powder, the carbon nanotube fiber and the graphene powder specifically comprises the following steps: 1) Impregnating the carbon nano tube fibers with a polyvinyl alcohol solution; 2) Placing graphene in an aqueous solution, and performing ultrasonic treatment to form uniformly dispersed graphene dispersion liquid; 3) Adding a dispersing agent acetone into the graphene dispersion liquid, adding carbon nano tube powder, continuing to carry out ultrasonic treatment, and uniformly stirring to obtain a mixed liquid; 4) Dispersing the infiltrated carbon nanotube fibers in the mixed solution, and finally concentrating and drying to obtain the compound conductive agent.
Step S25: firstly, placing polylactic acid and dispersant fatty acid polyol ester into a high-speed mixer to be fully mixed for 4min, so as 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: fully mixing the compound conductive agent and the first mixture in a high-speed mixer for 3min to obtain a third mixture;
step S28: placing the second mixture and the third mixture into a high-speed mixer, and fully mixing for 5min to obtain a mixture;
step S30: adding the mixed raw materials into a double screw extruder for granulation to obtain 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 host is 5HZ, and the vacuum degree is 0.08-0.09 MPa.
Example 2
The first aspect of the embodiment provides an antistatic polylactic acid material, which comprises 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, 1076.2 parts of antioxidant, 168.2 parts of antioxidant and 2 parts of talcum powder (5000 meshes).
The second aspect of the present embodiment provides a method for preparing an antistatic polylactic acid material, including the steps of:
step S10: 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, 0.2 part of antioxidant 1076, 168.2 parts of antioxidant and 2 parts of talcum powder (5000 meshes), the components are weighed.
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 the carbon nano tube fiber by ethanol solution; 2) Placing graphene in an aqueous solution, and performing ultrasonic treatment to form uniformly dispersed graphene dispersion liquid; 3) Adding ethyl acetate serving as a dispersing agent into the graphene dispersion liquid, adding carbon nano tube powder, continuing to carry out ultrasonic treatment, and uniformly stirring to obtain a mixed liquid; 4) Dispersing the infiltrated carbon nanotube fibers in the mixed solution, and finally concentrating and drying to obtain the compound conductive agent.
Step S25: firstly, placing polylactic acid and dispersant fatty acid amide into a high-speed mixer to be fully mixed for 4min, so as to obtain a first mixture;
step S26: placing the antioxidant 1076, 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: fully mixing the compound conductive agent and the first mixture in a high-speed mixer for 3min to obtain a third mixture;
step S28: placing the second mixture and the third mixture into a high-speed mixer, and fully mixing for 5min to obtain a mixture;
step S30: adding the mixed raw materials into a double screw extruder for granulation to obtain carbon nano tube modified antistatic polylactic acid granules. Wherein the temperature of the processing screw is 200-210 ℃, 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 host is 5HZ, and the vacuum degree is 0.08-0.09 MPa.
Example 3
The first aspect of the embodiment provides an antistatic polylactic acid material, 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, 0.2 part of antioxidant 1010, 0.2 part of antioxidant 168 and 2 parts of talcum powder (5000 meshes).
The second aspect of the present embodiment provides a method for preparing an antistatic polylactic acid material, including the steps of:
step S10: according to the 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 dispersing agent fatty acid polyol ester, 0.2 part of antioxidant 1010, 0.2 part of antioxidant 168, 2 parts of talcum powder (5000 meshes), and weighing the components.
Step S24: the step of mixing the carbon nanotube powder, the carbon nanotube fiber and the graphene powder specifically comprises the following steps: 1) Impregnating the carbon nano tube fibers with a polyvinyl alcohol solution; 2) Placing graphene in an aqueous solution, and performing ultrasonic treatment to form uniformly dispersed graphene dispersion liquid; 3) Adding dispersant ethanol into the graphene dispersion liquid, adding carbon nano tube powder, continuing to carry out ultrasonic treatment, and uniformly stirring to obtain a mixed liquid; 4) Dispersing the infiltrated carbon nanotube fibers in the mixed solution, and finally concentrating and drying to obtain the compound conductive agent.
Step S25: firstly, placing polylactic acid and dispersant fatty acid polyol ester into a high-speed mixer to be fully mixed for 4min, so as 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: fully mixing the compound conductive agent and the first mixture in a high-speed mixer for 3min to obtain a third mixture;
step S28: placing the second mixture and the third mixture into a high-speed mixer, and fully mixing for 5min to obtain a mixture;
step S30: adding the mixed raw materials into a double screw extruder for granulation to obtain carbon nano tube modified antistatic polylactic acid granules. Wherein the temperature of the processing screw is 200-210 ℃, 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 host is 5HZ, and the vacuum degree is 0.08-0.09 MPa.
Comparative example 1
A commercially available conventional polylactic acid material is provided in this comparative example.
Comparative example 2
The comparative example is different from example 1 in that the conductive agent is composed of carbon nanotube powder and graphene powder in a compound (1:1); the other operations are exactly the same.
Performance testing
The antistatic polylactic acid materials of examples 1 to 3 and comparative examples 1 and 2 were subjected to performance test, and the test results are shown in Table 1.
TABLE 1
| Numbering device | Impact strength KJ/m2 | Surface resistance omega | Onset melting Point |
| Example 1-2% conductive agent | 3.2 | 10 to the power of 6.9 | 162℃ |
| Example 2-3% conductive agent | 3.6 | 10 to the 5.0 th power | 165.5℃ |
| Example 3-3.5% conductive agent | 3.5 | 10 to the power of 4.5 | 165.3℃ |
| Comparative example 1 pure PLA | 2.9 | 10 to the power of 13.5 | 160℃ |
| Comparative example 2 | 3.1 | 10 to the power of 8.0 | 161℃ |
As can be seen from table 1, from examples 1 to 3, the mass ratio of the polylactic acid to the mixture of the carbon nanotube powder, the carbon nanotube fiber and the 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 all obviously improved, and in particular, compared with comparative example 1, the impact strength of the antistatic polylactic acid materials provided in examples 1 to 3 is increased, and the surface resistance and the initial melting point are improved. Among them, example 2 (the mass ratio of polylactic acid to carbon nanotube powder, carbon nanotube fiber and graphene powder mixture is 93.1:3) has the highest overall performance and cost efficiency. The conductive agent adopted in comparative example 2 is composed of carbon nanotube powder and graphene powder (1:1) in a compounding way, and the surface resistance of the prepared antistatic polylactic acid is increased, probably due to the lack of carbon nanotube fibers, and the integrity of a conductive network is reduced.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.
Claims (9)
1. The antistatic polylactic acid material is characterized by comprising the following components in parts by weight:
wherein the conductive agent comprises a mixture of carbon nanotube powder, carbon nanotube fiber and graphene powder;
the antistatic polylactic acid material comprises the following carbon nanotube powder, carbon nanotube fiber and graphene powder in parts by weight:
0.1 to 4 portions of carbon nano tube powder
1 to 4 portions of carbon nano tube fiber
0.1-3 parts of graphene powder;
the mass ratio of the carbon nanotube powder to the carbon nanotube fiber to the graphene powder is 2:1:1;
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;
the length of the carbon nano tube fiber is 300-1000 mu m, and the diameter is 50-100 mu m.
2. The antistatic polylactic acid material according to claim 1, wherein the dispersant comprises at least one of an aqueous nonionic fatty acid derivative dispersant and a silane coupling agent;
or/and the other auxiliary agents comprise at least one of antioxidant, auxiliary antioxidant and talcum powder.
3. The antistatic polylactic acid material according to claim 2, wherein said 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 an antioxidant 1010 and an antioxidant 1076;
or/and the auxiliary antioxidant comprises at least one of antioxidant 168, dilauryl thiodipropionate, octacosanol thiodipropionate and diphenyl octylphosphite;
or/and the particle size of the talcum powder is 500-10000 meshes.
4. The antistatic polylactic acid material according to claim 1 or 3, wherein the surface resistance of the antistatic polylactic acid material is 10 4 Ω～10 5 Ω。
5. The preparation method of the antistatic polylactic acid material is characterized by comprising the following steps:
weighing all raw material components according to the components contained in the antistatic polylactic acid material according to any one of claims 1 to 4;
mixing the raw material components to obtain a mixture;
and (3) carrying out melt mixing treatment on the mixture to obtain the antistatic polylactic acid material.
6. The method for preparing an antistatic polylactic acid material according to claim 5, wherein said mixing treatment comprises the steps of:
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 with the first mixture to obtain a third mixture;
mixing the second mixture and the third mixture to obtain a mixture;
or (b)
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, polylactic acid, the dispersing agent and the fourth mixture to obtain the mixture.
7. The method for producing an antistatic polylactic acid material according to claim 5 wherein said melt kneading process is a twin-screw extrusion process.
8. The method for preparing an antistatic polylactic acid material according to claim 7, wherein in the twin-screw extrusion process, 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.
9. The method for preparing an antistatic polylactic acid material according to claim 8, 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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