Graphene functional master batch and preparation method thereof

Abstract

The invention discloses a graphene functional master batch and a preparation method thereof. The preparation method comprises the following steps: uniformly dispersing graphene, antimony-doped tin dioxide and a dispersing aid in a specified solvent to obtain a graphene / functional material dispersion liquid; uniformly mixing the graphene / functional material dispersion liquid with plastic resin, and processing through a twin-screw process to obtain graphene functional master batches; wherein the specified solvent can dissolve the plastic resin under a heating condition. The graphene and the antimony-doped tin dioxide in the graphene functional master batch prepared by the method are uniformly dispersed in the plastic resin, so that the problems that the graphene and the antimony-doped tin dioxide are easy to agglomerate, poor in dispersion and non-uniform in mixing during processing and preparation of the graphene functional master batch are effectively solved.

Description

Technical Field

[0001] The present invention belongs to the technical field of plastic masterbatches, and in particular relates to a graphene functional masterbatch and a preparation method thereof. Background Art

[0002] Graphene, a new type of two-dimensional nanocarbon material, possesses exceptional properties, including high electrical and thermal conductivity, high specific surface area, and excellent mechanical properties. Antimony-doped tin dioxide (ATO) and indium tin oxide (ITO) powders, due to their high electrical conductivity and high infrared barrier properties, have broad application prospects in many fields and have rapidly developed as new functional materials in recent years. Mixing graphene, ATO, or ITO with plastics to prepare masterbatches, which can then be used to manufacture various functional plastic materials, such as films, or to spin functional fibers from the masterbatches, are currently hot topics in both industry and academia. However, these applications currently face challenges: mixing graphene, ATO, or ITO powders with plastics can lead to powder agglomeration and poor dispersion. Conventional solid-phase high-speed blending and screw extrusion methods make it difficult to evenly disperse the inorganic powders in the plastic resin matrix, compromising the subsequent processing performance of the product. This also hinders the full utilization of the excellent properties of graphene and ATO in the masterbatch's end-use applications.

[0003] Existing patent CN105037754A discloses a process for preparing uniformly dispersed functional polyester masterbatch using a slurry method. This process uses ethanol as a solvent to disperse inorganic powder, then adds polyester powder and other additives, disperses and mixes to form a slurry, and then dries, pulverizes, melts, and extrudes into granules. A disadvantage of this patented process is that ethanol cannot dissolve polyester, and the dispersed inorganic powder can only be coated on the surface of the polyester powder, which is much larger than itself. This unevenness in the polyester powder particle size also affects the uniformity of the inorganic powder dispersion in the polyester masterbatch. In addition, ethanol has a boiling point of less than 80°C, which is too low compared to the 100°C or higher temperatures required for twin-screw extrusion. As a result, the ethanol solvent evaporates quickly during twin-screw extrusion, and the polyester powder can only form a high-viscosity melt at high temperatures, unable to form a lower-viscosity solution or semi-solution state with the help of a solvent. The high viscosity hinders the dispersion of the inorganic powder in the masterbatch, making it difficult for the inorganic powder to be evenly distributed within the masterbatch, and the masterbatch's performance cannot be fully and effectively utilized.

[0004] Therefore, it is particularly important to solve the problem of graphene and ATO being easily agglomerated and poorly dispersed during the processing and preparation of masterbatches. Summary of the Invention

[0005] The main purpose of the present invention is to provide a graphene functional masterbatch and its preparation method, aiming to solve the problem of graphene and ATO being easily agglomerated and poorly dispersed during the processing and preparation of the masterbatch, thereby overcoming the shortcomings of the existing technology.

[0006] To achieve the aforementioned object of the invention, the technical solutions adopted by the present invention include:

[0007] One aspect of the present invention provides a method for preparing a graphene functional masterbatch, comprising: uniformly dispersing graphene, a functional material, and a dispersing aid in a specified solvent to obtain a graphene / functional material dispersion;

[0008] The graphene / functional material dispersion is evenly mixed with a plastic resin, and processed by a twin-screw process to obtain a graphene functional masterbatch; wherein the designated solvent can dissolve the plastic resin under heating conditions, and the functional material includes any one of antimony-doped tin dioxide and indium tin oxide.

[0009] Furthermore, the designated solvent includes any one or a combination of two or more of dimethylformamide, cyclohexanone, and propylene glycol methyl ether acetate.

[0010] Furthermore, the designated solvent can dissolve the plastic resin under heating conditions of 80 to 200°C.

[0011] Another aspect of the present invention provides a graphene functional masterbatch obtained by the preparation method, wherein the graphene and the functional material in the graphene functional masterbatch are uniformly dispersed in the plastic resin.

[0012] Another aspect of the present invention provides a three-dimensional functional composite material made from the graphene functional masterbatch.

[0013] Another aspect of the present invention also provides the use of the graphene functional masterbatch or the three-dimensional functional composite material in the field of far-infrared temperature-rising fabrics.

[0014] Compared with the prior art, the present invention has at least the following beneficial effects:

[0015] (1) The designated solvent of the present invention can dissolve the plastic resin used to prepare the graphene functional masterbatch. When the graphene functional masterbatch is processed by the twin-screw process, the molten plastic resin and the dispersion liquid form a semi-solution fusion state under the action of the solvent. Nano-graphene and ATO particles are evenly dispersed in the plastic resin, solving the problem of easy agglomeration, poor dispersion, and uneven mixing of graphene and ATO in the processing and preparation of graphene functional masterbatch.

[0016] (2) The three-dimensional functional composite material composed of two-dimensional graphene material and zero-dimensional functional materials such as ATO and ITO combines the high carrier mobility characteristics of functional materials such as graphene and ATO, thereby achieving higher functionality. The three-dimensional functional composite material prepared can be used as a far-infrared temperature rise fabric with a higher far-infrared temperature rise. DETAILED DESCRIPTION

[0017] In view of the above problems existing in the prior art, the inventors of the present invention have conducted extensive and in-depth research and provide a method for preparing graphene functional masterbatch.

[0018] The technical solution, its implementation process and principles are further explained below.

[0019] As one aspect of the technical solution of the present invention, a method for preparing a graphene functional masterbatch is provided, comprising: uniformly dispersing graphene, a functional material, and a dispersing aid in a specified solvent to obtain a graphene / functional material dispersion;

[0020] The graphene / functional material dispersion is evenly mixed with a plastic resin, and processed by a twin-screw process to obtain a graphene functional masterbatch; wherein the designated solvent can dissolve the plastic resin under heating conditions, and the functional material includes any one of antimony-doped tin dioxide and indium tin oxide.

[0021] In some embodiments, the designated solvent includes any one or a combination of two or more of dimethylformamide, cyclohexanone, and propylene glycol methyl ether acetate.

[0022] In some embodiments, the designated solvent is capable of dissolving the plastic resin under heating conditions of 80-200°C.

[0023] In the present invention, the mechanism by which the designated solvent can dissolve the plastic resin under heating conditions is that after the plastic resin is heated to a viscous flow state, the designated solvent is an organic solvent that can dissolve plastic macromolecules and simultaneously uniformly disperse graphene, ATO, or ITO in the plastic resin, thereby solving the common agglomeration problem existing in the mixing of nanopowders and plastics, and obtaining a nanomaterial-filled plastic functional masterbatch with good dispersion.

[0024] In some embodiments, the graphene is few-layer graphene with 1 to 20 layers.

[0025] In some embodiments, the antimony-doped tin dioxide includes SnO2 and SbO2, and the mass ratio of SnO2 to SbO2 is 95-80:5-20.

[0026] In some embodiments, the indium tin oxide includes InO2 and SnO2, and the mass ratio of InO2 to SnO2 is 98-90:2-10.

[0027] In some embodiments, the dispersant comprises a BYK dispersant.

[0028] In some preferred embodiments, the dispersant includes at least any one of BYK-9756, BYK-2050, BYK-2055, etc., but is not limited thereto.

[0029] In some embodiments, the plastic resin includes at least any one of polybutylene terephthalate (PBT), thermoplastic polyurethane (TPU), polyacrylonitrile (PAN), etc., but is not limited thereto.

[0030] In some embodiments, in the graphene / functional material dispersion, the mass fraction of graphene is 5-20%, the mass fraction of functional material is 5-20%, and the mass fraction of dispersing aid is 1-5%, calculated in mass percentage.

[0031] In some embodiments, based on the dry mass of graphene + functional material, the mass ratio of graphene + functional material to plastic resin in the graphene functional masterbatch is 10-25:90-75.

[0032] In some embodiments, the method for preparing the graphene functional masterbatch specifically includes: grinding and dispersing the graphene, antimony-doped tin dioxide and a dispersing aid in a specified solvent to obtain a nano-scale graphene / functional material dispersion.

[0033] Furthermore, the particle size distribution of graphene in the graphene / functional material dispersion is 1000 to 5000 nm, and the particle size distribution of the functional material is 50 to 500 nm.

[0034] In some embodiments, the preparation method of the graphene functional masterbatch specifically further includes: uniformly mixing the nano-scale graphene / functional material dispersion with a plastic resin, and obtaining the graphene functional masterbatch through a twin-screw process; wherein the designated solvent can dissolve the plastic resin under heating conditions of 80 to 235°C.

[0035] Furthermore, the designated solvent can dissolve the plastic resin under heating conditions of 80-200°C.

[0036] Furthermore, the screw extrusion temperature of the twin-screw process is 100-180°C in the first zone, 120-200°C in the second zone, 170-230°C in the third zone, 175-235°C in the fourth zone, 175-235°C in the fifth zone, 175-235°C in the sixth zone, 175-235°C in the seventh zone, 170-230°C in the eighth zone, and 165-235°C in the ninth zone.

[0037] Furthermore, the processing time is 3 to 10 minutes.

[0038] In some more specific embodiments, the method for preparing the graphene functional masterbatch may specifically include the following steps:

[0039] S1. Preparing a graphene / ATO dispersion, wherein the graphene content is 5-20%, the ATO content is 5-20%, the dispersant is BYK, the dispersant dosage is 1-5%, and the remainder is a specified solvent, adding the graphene / ATO dispersion to the specified solvent, and subjecting the uniformly stirred dispersion to ultrafine grinding to obtain a graphene / functional material dispersion with excellent dispersibility;

[0040] S2. The graphene / functional material dispersion obtained in step S1 is mixed with plastic resin particles in a mixing ratio calculated based on the dry mass of graphene + functional material: graphene + functional material: plastic resin = 10-25:90-75, and the graphene functional masterbatch is obtained by twin-screw extrusion. The screw extrusion temperature is 100-180° C. in the first zone, 120-200° C. in the second zone, 170-230° C. in the third zone, 175-235° C. in the fourth zone, 175-235° C. in the fifth zone, 175-235° C. in the sixth zone, 175-235° C. in the seventh zone, 170-230° C. in the eighth zone, and 165-235° C. in the ninth zone. The water cooling temperature is 8° C., and the processing time is 3-10 min. The designated solvent can dissolve the plastic resin under heating conditions of 80-235° C.

[0041] As another aspect of the technical solution of the present invention, a graphene functional masterbatch obtained by the preparation method is provided, in which graphene and antimony-doped tin dioxide are uniformly dispersed in a plastic resin.

[0042] Furthermore, the volume resistivity of the graphene functional masterbatch is not greater than 10 8 Ω.cm.

[0043] Furthermore, the graphene functional masterbatch has a filtration pressure value of no more than 1.0 bar / g through a 400-mesh filter.

[0044] As one aspect of the technical solution of the present invention, a three-dimensional functional composite material prepared from the graphene functional masterbatch is provided.

[0045] As one aspect of the technical solution of the present invention, it also provides the application of the graphene functional masterbatch or the three-dimensional functional composite material in the field of far-infrared temperature-rising fabrics.

[0046] In summary, the solvent selected when preparing the graphene / ATO dispersion in the present invention can dissolve the plastic resin used to prepare the graphene functional masterbatch. When the graphene functional masterbatch is processed by the twin-screw process, the molten plastic resin and the dispersion form a semi-solution fusion state under the action of the solvent, and the nano-graphene and ATO particles are uniformly dispersed in the plastic resin, solving the problems of easy agglomeration, poor dispersion, and uneven mixing of graphene and ATO in the processing and preparation of graphene functional masterbatch.

[0047] In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with embodiment. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. Those skilled in the art will make modifications or equivalent substitutions based on understanding the technical solution of the present invention, without departing from the spirit and scope of the technical solution of the present invention, and all should be encompassed within the protection scope of the present invention.

[0048] Where specific experimental procedures or conditions are not specified in the examples, the experiments were carried out according to conventional experimental procedures or conditions described in literature in the field. Reagents or instruments used without manufacturer specified are commercially available. Commercially available options for other raw materials and instruments not mentioned are conventional and do not relate to the core technical means of the present invention.

[0049] Example 1

[0050] S1. Prepare a graphene / ATO dispersion, wherein the graphene content is 20%, the ATO content is 5%, the dispersant is BYK-9756, the dispersant dosage is 1.5%, and the rest is solvent, the solvent ratio is a mixture of dimethylformamide: cyclohexanone: propylene glycol methyl ether acetate = 1:1.5:2.5, and after ultrafine grinding the uniformly stirred dispersion, obtain a few-layer graphene / ATO high-concentration slurry with excellent dispersion performance;

[0051] S2. The high-concentration slurry obtained in S1 is mixed with polybutylene terephthalate particles. The mixing ratio is calculated based on the dry mass of graphene + ATO, graphene + ATO: polybutylene terephthalate = 1:9. The polybutylene terephthalate masterbatch of graphene / ATO is obtained by twin-screw extrusion. The screw extrusion temperature is: 150°C in the first zone, 180°C in the second zone, 210°C in the third zone, 220°C in the fourth zone, 225°C in the fifth zone, 225°C in the sixth zone, 225°C in the seventh zone, 210°C in the eighth zone, 180°C in the ninth zone, and the water cooling temperature is 8°C.

[0052] The filtration pressure value of 400 mesh filter is 0.92 bar / g (tested according to EN 13900-5:2021 standard). The volume resistivity of the obtained masterbatch is 10 8 Ω.cm.

[0053] Example 2

[0054] S1. preparing a graphene / ITO dispersion, wherein the graphene content is 20%, the ITO content is 5%, the dispersant is BYK-2050, the dispersant dosage is 2.0%, and the remainder is a solvent, the solvent ratio is a mixture of dimethylformamide and cyclohexanone = 2:1, and the uniformly stirred dispersion is subjected to ultrafine grinding to obtain a high-concentration few-layer graphene / ITO slurry with excellent dispersion performance;

[0055] S2. The high-concentration slurry obtained in S1 is mixed with polyacrylonitrile particles. The mixing ratio is calculated as graphene + ITO: polyacrylonitrile = 1:9 based on the dry mass of graphene + ITO. The graphene / ITO polyacrylonitrile masterbatch is obtained by twin-screw extrusion. The screw extrusion temperature is: 180°C in the first zone, 200°C in the second zone, 220°C in the third zone, 230°C in the fourth zone, 235°C in the fifth zone, 235°C in the sixth zone, 235°C in the seventh zone, 230°C in the eighth zone, 225°C in the ninth zone, and the water cooling temperature is 8°C.

[0056] The filter pressure value of 400 mesh filter is 0.85 bar / g (tested according to EN 13900-5:2021 standard). The volume resistivity of the obtained masterbatch is 10 8 Ω.cm.

[0057] Example 3

[0058] S1. Prepare a graphene / ATO dispersion, wherein the graphene content is 5%, the ATO content is 20%, the dispersant is BYK-2055, the dispersant dosage is 5.0%, and the remainder is a solvent, the solvent ratio is a mixture of dimethylformamide: cyclohexanone: propylene glycol methyl ether acetate = 1:1:3, and after ultrafine grinding the uniformly stirred dispersion, obtain a few-layer graphene / ATO high-concentration slurry with excellent dispersion performance;

[0059] S2. The high-concentration slurry obtained in S1 is mixed with thermoplastic polyurethane elastomer rubber particles. The mixing ratio is calculated based on the dry mass of graphene + ATO, i.e., graphene + ATO: thermoplastic polyurethane elastomer rubber = 1:4. The graphene / ATO thermoplastic polyurethane elastomer rubber masterbatch is obtained by twin-screw extrusion. The screw extrusion temperatures are: 105°C in the first zone, 120°C in the second zone, 150°C in the third zone, 160°C in the fourth zone, 160°C in the fifth zone, 175°C in the sixth zone, 175°C in the seventh zone, 170°C in the eighth zone, and 145°C in the ninth zone. The water cooling temperature is 5°C.

[0060] The filter pressure value of 400 mesh filter is 0.55 bar / g (tested according to EN 13900-5:2021 standard). The volume resistivity of the obtained masterbatch is 10 6 Ω.cm.

[0061] Example 4

[0062] S1. Prepare a graphene / ITO dispersion, wherein the graphene content is 10%, the ITO content is 15%, the dispersant is BYK-2055, the dispersant dosage is 5.0%, and the remainder is a solvent, the solvent ratio is a mixture of dimethylformamide: cyclohexanone: propylene glycol methyl ether acetate = 2:1:2, and the uniformly stirred dispersion is subjected to ultrafine grinding to obtain a high-concentration few-layer graphene / ITO slurry with excellent dispersion performance;

[0063] S2. The high-concentration slurry obtained in S1 is mixed with butylene terephthalate particles. The mixing ratio is calculated based on the dry mass of graphene + ITO, graphene + ITO: thermoplastic polyurethane elastomer rubber = 1:4. The graphene / ITO butylene terephthalate masterbatch is obtained by twin-screw extrusion. The screw extrusion temperature is: 130°C in the first zone, 160°C in the second zone, 190°C in the third zone, 210°C in the fourth zone, 225°C in the fifth zone, 225°C in the sixth zone, 215°C in the seventh zone, 195°C in the eighth zone, 160°C in the ninth zone, and the water cooling temperature is 5°C.

[0064] The filtration pressure value of 400 mesh filter is 0.58 bar / g (tested according to EN 13900-5:2021 standard). The volume resistivity of the obtained masterbatch is 10 5 Ω.cm.

[0065] Example 5

[0066] S1. Prepare a graphene / ATO dispersion, wherein the graphene content is 15%, the ATO content is 10%, the dispersant is BYK-9756, the dispersant dosage is 3.5%, and the remainder is a solvent, the solvent ratio is a mixture of dimethylformamide: cyclohexanone: propylene glycol methyl ether acetate = 1:2:2, and the uniformly stirred dispersion is subjected to ultrafine grinding to obtain a high-concentration few-layer graphene / ATO slurry with excellent dispersion performance;

[0067] S2. The high-concentration slurry obtained in S1 is mixed with thermoplastic polyurethane elastomer rubber particles. The mixing ratio is calculated as graphene + ATO: thermoplastic polyurethane elastomer rubber = 1:9 based on the dry mass of graphene + ATO. The graphene / ATO thermoplastic polyurethane elastomer rubber masterbatch is obtained by twin-screw extrusion. The screw extrusion temperature is: 110°C in the first zone, 130°C in the second zone, 150°C in the third zone, 160°C in the fourth zone, 160°C in the fifth zone, 175°C in the sixth zone, 175°C in the seventh zone, 170°C in the eighth zone, 145°C in the ninth zone, and the water cooling temperature is 5°C.

[0068] The filter pressure value of 400 mesh filter is 0.40 bar / g (tested according to EN 13900-5:2021 standard). The volume resistivity of the obtained masterbatch is 10 8 Ω.cm.

[0069] Example 6

[0070] The operating steps are the same as those in Example 5, except that the screw extrusion temperatures are: 80°C in the first zone, 110°C in the second zone, 140°C in the third zone, 170°C in the fourth zone, 185°C in the fifth zone, 200°C in the sixth zone, 200°C in the seventh zone, 200°C in the eighth zone, 190°C in the ninth zone, and the water cooling temperature is 5°C.

[0071] The filter pressure value of 400 mesh filter is 0.35 bar / g (tested according to EN 13900-5:2021 standard). The volume resistivity of the obtained masterbatch is 10 8 Ω.cm.

[0072] Comparative Example 1

[0073] S1. Prepare a graphene / ITO dispersion, wherein the graphene content is 20%, the ITO content is 5%, the dispersant is BYK-2050, the dispersant dosage is 2.0%, and the rest is ethanol as solvent. After the uniformly stirred dispersion is subjected to ultrafine grinding, a high-concentration few-layer graphene / ITO slurry with excellent dispersion performance is obtained;

[0074] S2. The high-concentration slurry obtained in S1 was mixed with polyacrylonitrile particles. The mixing ratio was calculated based on the dry mass of graphene + ITO, graphene + ITO: polyacrylonitrile = 1:9. The graphene / ITO polyacrylonitrile masterbatch was obtained by twin-screw extrusion. The screw extrusion temperature was: 160°C in the first zone, 180°C in the second zone, 210°C in the third zone, 230°C in the fourth zone, 235°C in the fifth zone, 235°C in the sixth zone, 220°C in the seventh zone, 205°C in the eighth zone, and 180°C in the ninth zone. The water cooling temperature was 5°C. The volume resistivity of the obtained masterbatch was 10 10 Ω.cm, 400 mesh filter pressure value is 3.26 bar / g (tested according to EN 13900-5:2021 standard).

[0075] Comparative Example 2

[0076] A semi-solution method for preparing graphene functional masterbatch is characterized by comprising the following steps:

[0077] S1. preparing a graphene dispersion, wherein the graphene content is 25%, the dispersant is BYK-9756, the dispersant dosage is 2.5%, and the rest is propylene glycol methyl ether as solvent, and the uniformly stirred dispersion is subjected to ultrafine grinding to obtain a high-concentration slurry of few-layer graphene with excellent dispersion performance;

[0078] S2. The high-concentration slurry obtained in S1 is mixed with thermoplastic polyurethane elastomer rubber particles. The mixing ratio is calculated as graphene: thermoplastic polyurethane elastomer rubber = 1:4 based on the dry mass of graphene. The graphene polybutylene terephthalate masterbatch is obtained by twin-screw extrusion. The screw extrusion temperature is: 100°C in the first zone, 130°C in the second zone, 150°C in the third zone, 160°C in the fourth zone, 160°C in the fifth zone, 175°C in the sixth zone, 175°C in the seventh zone, 170°C in the eighth zone, 140°C in the ninth zone, and the water cooling temperature is 8°C.

[0079] The volume resistivity of the obtained masterbatch is 10 10 Ω.cm, 400 mesh filter pressure value is 2.56 bar / g (tested according to EN13900-5:2021 standard).

[0080] Comparative Example 3

[0081] S1. Prepare a graphene / ATO dispersion, wherein the graphene content is 5%, the ATO content is 20%, the dispersant is BYK-2050, the dispersant dosage is 4.0%, and the rest is propylene glycol methyl ether acetate solvent. After the uniformly stirred dispersion is subjected to ultrafine grinding, a high-concentration ATO slurry with excellent dispersion performance is obtained;

[0082] S2. The high-concentration slurry obtained in S1 is mixed with butylene terephthalate particles. The mixing ratio is calculated based on the dry mass of graphene + ATO, i.e., graphene + ATO: butylene terephthalate = 1:9. The graphene / ATO butylene terephthalate masterbatch is obtained by twin-screw extrusion. The screw extrusion temperature is: 180°C in the first zone, 200°C in the second zone, 230°C in the third zone, 235°C in the fourth zone, 235°C in the fifth zone, 235°C in the sixth zone, 235°C in the seventh zone, 230°C in the eighth zone, 225°C in the ninth zone, and the water cooling temperature is 8°C.

[0083] In this comparative example, the volume resistivity of the obtained masterbatch is 10 9 Ω.cm, 400 mesh filter pressure value is 0.35 bar / g (tested according to EN 13900-5:2021 standard).

[0084] Comparative Example 4

[0085] The operation steps are the same as those in Example 1, except that the screw extrusion temperature is 70° C. throughout the entire process. Since the screw extrusion temperature is lower than 80° C., the plastic resin cannot be processed.

[0086] Application Example 1

[0087] The polyester fabric spun with 6% of the graphene masterbatch of Example 1 has an infrared emissivity of 0.7592 and a maximum infrared temperature rise of 5.2° C. when used as a fabric.

[0088] Application Example 2

[0089] The acrylic fabric spun with 6% of the graphene masterbatch of Example 2 has an infrared emissivity of 0.6590 and a maximum infrared temperature rise of 6.3° C. when used as a fabric.

[0090] Application Example 3

[0091] The spandex fabric spun with 6% of the graphene masterbatch of Example 3 has an infrared emissivity of 0.90 and a maximum infrared temperature rise of 5.8° C. when used as a fabric.

[0092] Application Example 4

[0093] Since the ethanol solvent cannot dissolve the plastic resin and the graphene agglomerates, the graphene masterbatch of Comparative Example 1 with 3% and 6% addition has serious filaments and poor melt pressure, and is not spinnable.

[0094] Application Example 5

[0095] The spandex fabric spun with 6% of the graphene masterbatch of Comparative Example 2 has a far-infrared emissivity of 0.90 and a maximum infrared temperature rise of 2.6°C.

[0096] Application Example 6

[0097] The fabric spun from the butylene terephthalate masterbatch with 6% of the graphene / ATO of Comparative Example 3 had an infrared emissivity of 0.91 and a maximum infrared temperature rise of 3.9° C. when used as a fabric.

[0098] The various aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and are not intended to limit the present invention, the scope of which is defined solely by the claims. Other embodiments, modifications and uses will be apparent to those skilled in the art without departing from the spirit and scope of the invention as claimed.

[0099] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments using other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0100] Although the present invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions, and / or additions may be made and that substantial equivalents may be substituted for elements of the described embodiments without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the present invention without departing from the scope of the invention. Therefore, it is not intended that the present invention be limited to the specific embodiments disclosed for carrying out the invention, but it is intended that the invention encompass all embodiments falling within the scope of the appended claims.

Claims

1. A method for preparing graphene functional masterbatch, characterized in that: include: Evenly dispersing graphene, functional materials, and a dispersing aid in a designated solvent to obtain a graphene / functional material dispersion; The graphene / functional material dispersion is evenly mixed with a plastic resin, and processed by a twin-screw process to obtain a graphene functional masterbatch; wherein the designated solvent can dissolve the plastic resin under heating conditions, and the functional material includes any one of antimony-doped tin dioxide and indium tin oxide.

2. The preparation method according to claim 1, wherein: The designated solvent includes any one or a combination of two or more of dimethylformamide, cyclohexanone, and propylene glycol methyl ether acetate; And / or, the designated solvent is capable of dissolving the plastic resin under heating conditions of 80-200°C.

3. The preparation method according to claim 1, wherein: The graphene includes few-layer graphene, with the number of layers being 1 to 20; And / or, the antimony-doped tin dioxide comprises SnO2 and SbO2, and the mass ratio of SnO2 to SbO2 is 95-80:5-20; And / or, the indium tin oxide comprises InO2 and SnO2, and the mass ratio of InO2 to SnO2 is 98-90:2-10; and / or, the dispersant comprises a BYK dispersant; Preferably, the dispersant includes at least any one of BYK-9756, BYK-2050, and BYK-2055; And / or, the plastic resin includes at least any one of polybutylene terephthalate, polyethylene terephthalate, thermoplastic polyurethane elastomer rubber, polyacrylonitrile, and polyamide 66.

4. The preparation method according to claim 1, wherein: In terms of mass percentage, in the graphene / functional material dispersion, the mass fraction of graphene is 5-20%, the mass fraction of the functional material is 5-20%, and the mass fraction of the dispersing aid is 1-5%; And / or, based on the dry mass of graphene + functional material, the mass ratio of graphene + functional material to plastic resin in the graphene functional masterbatch is 10-25:90-75.

5. The preparation method according to claim 1, characterized in that Specifically include: Grinding and dispersing the graphene, antimony-doped tin dioxide and a dispersing aid in a specified solvent to obtain a nano-scale graphene / functional material dispersion; Preferably, the particle size distribution of the graphene in the graphene / functional material dispersion is 1000 to 5000 nm, and the particle size distribution of the functional material is 50 to 500 nm.

6. The preparation method according to claim 5, characterized in that Specifically include: The nano-scale graphene / functional material dispersion is uniformly mixed with a plastic resin, and processed by a twin-screw process to obtain a graphene functional masterbatch; wherein the specified solvent can dissolve the plastic resin under heating conditions of 80 to 235° C.; Preferably, the designated solvent is capable of dissolving the plastic resin under heating conditions of 80 to 200°C; Preferably, the screw extrusion temperature of the twin-screw process is 100-180°C in the first zone, 120-200°C in the second zone, 170-230°C in the third zone, 175-235°C in the fourth zone, 175-235°C in the fifth zone, 175-235°C in the sixth zone, 175-235°C in the seventh zone, 170-230°C in the eighth zone, and 165-235°C in the ninth zone; Preferably, the processing time is 3 to 10 minutes.

7. The graphene functional masterbatch obtained by the preparation method according to any one of claims 1 to 6, characterized in that: In the graphene functional masterbatch, graphene and functional materials are uniformly dispersed in the plastic resin.

8. The graphene functional masterbatch according to claim 7, characterized in that: The volume resistivity of the graphene functional masterbatch is not greater than 10 8 Ω.cm; And / or, the graphene functional masterbatch has a filtration pressure value of no more than 1.0 bar / g through a 400-mesh filter.

9. A three-dimensional functional composite material prepared from the graphene functional masterbatch according to claim 7 or 8.

10. Use of the graphene functional masterbatch according to claim 7 or 8 or the three-dimensional functional composite material according to claim 9 in the field of far-infrared temperature-rising fabrics.