Graphene modified functional master batch and preparation method thereof

Abstract

The invention relates to a graphene modified functional master batch and a preparation method thereof. The master batch is prepared from the following components in parts by weight: 10 to 18 parts of basic thermoplastic resin, 8 to 12 parts of composite graphene slurry prepared by a physical method, 12 to 15 parts of conductive filler, 0.2 to 0.6 part of phthalate, 0.2 to 0.8 part of antioxidant, 0.5 to 1 part of flocculating agent, 1 to 2 parts of stabilizer, 0.5 to 1 part of aluminate coupling agent and 1 to 2 parts of talcum powder, according to the invention, the conductive, antistatic, bactericidal and bacteriostatic properties of textile fibers can be improved, and compared with carbon black type conductive master batch, the fibers spun by using the product are light in color and gray, and can be dyed or directly spun into colored yarns, so that the mechanical properties of the spun fibers and plastics can be effectively enhanced, and the economic added value of the product is further improved.

Description

Technical Field

[0001] The invention relates to the technical field of polymer modified materials, and in particular to a graphene modified functional masterbatch and a preparation method thereof. Background Art

[0002] Traditional thermoplastic resin materials (such as PA, PP, PE) are widely used in textiles, high-strength plastics and other fields due to their wear resistance, toughness, stability and easy processing and molding. With the continuous development of science and technology, the requirements for material performance in various fields are increasing day by day. Traditional thermoplastic resin masterbatch can no longer meet the current production and life needs of people, such as antistatic, UV resistance, antibacterial and antibacterial properties and excellent mechanical properties.

[0003] In order to improve the performance of traditional thermoplastic resin materials, the introduction of nanomaterials to enhance their mechanical properties and durability has been widely mentioned; the discovery of graphene, due to its large surface area and high reactivity, enables it to be combined with other materials to form nanocomposites. At the same time, other nano-conductive filler materials are introduced to synergistically enhance and improve the stability of traditional thermoplastic resin materials molecules, thereby increasing their added value and further broadening their development and application prospects.

[0004] At present, most of the traditional thermoplastic resin masterbatch modification uses graphene oxide. The introduced metal atoms or oxygen-containing functional groups destroy the original properties of graphene (such as electrical properties, mechanical properties, and molecular assembly properties) to a certain extent, and its structural defects have a certain impact on the improvement of the mechanical properties and conductive properties of the thermoplastic resin masterbatch. This technical solution is to study the modification of plastic resin masterbatch with graphene prepared by physical method. Summary of the invention

[0005] Based on this, the purpose of the present invention is to provide a graphene-modified functional masterbatch and a preparation method thereof that can effectively improve the mechanical properties of traditional thermoplastic resin masterbatch and increase its economic added value.

[0006] To achieve the above object, the technical solution of the present invention is as follows: A graphene-modified functional masterbatch, characterized in that the masterbatch consists of the following components by weight: 10-18 parts of a basic thermoplastic resin, 8-12 parts of a composite graphene slurry prepared by a physical method, 12-15 parts of a conductive filler, 0.2-0.6 parts of a phthalate, 0.2-0.8 parts of an antioxidant, 0.5-1 parts of a flocculant, 1-2 parts of a stabilizer, 0.5-1 parts of an aluminate coupling agent, and 1-2 parts of talc.

[0007] As a preferred technical solution, the base thermoplastic resin may be polyamide resin, polyethylene resin or polypropylene resin.

[0008] As a preferred technical solution, the composite graphene slurry is prepared by stirring and ultrasonicating a few-layer graphene powder with a solid content of 3% and a multi-layer graphene powder with a solid content of 5% in a PVA+PVP dispersion system, respectively, wherein the ratio of the graphene slurry prepared from the few-layer graphene powder to the graphene slurry prepared from the multi-layer graphene powder is 3:7.

[0009] As a preferred technical solution, the graphene powder is prepared from expandable graphite and pure water by a physical method, wherein the number of layers of the few-layer graphene powder is 2-5 and the particle size (D50) is distributed between 4um-6um, and the number of layers of the multi-layer graphene powder is 5-10 and the particle size (D50) is distributed between 8um-12um.

[0010] As a preferred technical solution, the conductive filler is prepared by compounding and dispersing single-walled carbon nanotube conductive slurry and dendritic graphene powder in a mass ratio of 1:0.6-0.8.

[0011] As a preferred technical solution, the antioxidant is a mixture of antioxidant 168, antioxidant 1076 and didodecanol thiodipropionate in a weight ratio of 6:3:1.

[0012] As a preferred technical solution, the stabilizer is at least one of sodium stearate and diphenyl phosphite; and the flocculant is polyacrylamide.

[0013] A method for preparing a graphene-modified functional masterbatch, characterized in that it comprises the following steps: S1: weighing composite graphene slurry and conductive filler by weight into a stirring container, stirring for 30-60 minutes, adding 50-80 parts by weight of polyhydroxy acid water reducer during the stirring process, and drying after being completely mixed to obtain a mixture 1; S2: feeding a base thermoplastic resin into a melting device, and sequentially adding phthalate, a flocculant and a stabilizer weighed in parts by weight during the melting process to mix the mixture to obtain a mixture 2; S3: Putting the mixed material 2, the mixed dry material 1, the antioxidant, the aluminate coupling agent and the talc powder into a granulator in sequence for mixing and granulation, thereby obtaining the graphene-modified functional masterbatch.

[0014] As a preferred technical solution, the granulation particle size in step three is 1 mm to 3 mm.

[0015] The beneficial effects of the present invention are: 1. Improving the conductivity, antistatic, bactericidal and antibacterial properties of textile fibers; 2. Having good ultraviolet protection function; 3. Compared with carbon black conductive masterbatch, the fiber spun by using this product is lighter in color, gray, and can be dyed or directly spun into colored yarn; 4. It can effectively enhance the mechanical properties of spun fibers and plastics, thereby improving the economic added value of the products. DETAILED DESCRIPTION

[0016] In order to further understand and appreciate the technical means and effects achieved by the present invention, a preferred embodiment is described in detail as follows: Example

[0017] A graphene-modified functional masterbatch consists of the following components by weight: 18 parts of a basic thermoplastic resin, 8 parts of a composite graphene slurry prepared by a physical method, 15 parts of a conductive filler, 0.6 parts of phthalate, 0.8 parts of an antioxidant, 1 part of a flocculant, 2 parts of a stabilizer, 1 part of an aluminate coupling agent, and 2 parts of talc.

[0018] In this embodiment, the base thermoplastic resin may be a polyamide resin, a polyethylene resin, or a polypropylene resin.

[0019] In this embodiment, the composite graphene slurry is prepared by stirring and ultrasonicating a few-layer graphene powder with a solid content of 3% and a multi-layer graphene powder with a solid content of 5% in a PVA+PVP dispersion system, respectively, wherein the ratio of the graphene slurry prepared from the few-layer graphene powder to the graphene slurry prepared from the multi-layer graphene powder is 3:7.

[0020] In this embodiment, graphene powder is prepared from expandable graphite and pure water by a physical method, wherein the number of layers of the few-layer graphene powder is 2-5 and the particle size (D50) is distributed between 4um-6um, and the number of layers of the multi-layer graphene powder is 5-10 and the particle size (D50) is distributed between 8um-12um.

[0021] In this embodiment, the conductive filler is prepared by mixing and dispersing single-walled carbon nanotube conductive paste and dendritic graphene powder in a mass ratio of 1:0.8.

[0022] In this embodiment, the antioxidant is a mixture of antioxidant 168, antioxidant 1076 and didodecanol thiodipropionate in a weight ratio of 6:3:1.

[0023] In this embodiment, the stabilizer is at least one of sodium stearate and diphenyl phosphite; the flocculant is polyacrylamide A method for preparing a graphene-modified functional masterbatch comprises the following steps: S1: weighing composite graphene slurry and conductive filler by weight into a stirring container, stirring for 30-60 minutes, adding 50-80 parts by weight of polyhydroxy acid water reducer during the stirring process, and drying after being completely mixed to obtain a mixture 1; S2: feeding a base thermoplastic resin into a melting device, and sequentially adding phthalate, a flocculant and a stabilizer weighed in parts by weight during the melting process to mix the mixture to obtain a mixture 2; S3: Putting the mixed material 2, the mixed dry material 1, the antioxidant, the aluminate coupling agent and the talc powder into a granulator in sequence for mixing and granulation, thereby obtaining the graphene-modified functional masterbatch.

[0024] In this embodiment, the granulation particle size in the above step three is 1 mm to 3 mm. Example

[0025] A graphene-modified functional masterbatch consists of the following components in parts by weight: 16 parts of a basic thermoplastic resin, 9 parts of a composite graphene slurry prepared by a physical method, 14 parts of a conductive filler, 0.5 parts of a phthalate, 0.6 parts of an antioxidant, 0.8 parts of a flocculant, 1.6 parts of a stabilizer, 0.8 parts of an aluminate coupling agent, and 1.6 parts of talc.

[0026] In this embodiment, the base thermoplastic resin may be a polyamide resin, a polyethylene resin, or a polypropylene resin.

[0027] In this embodiment, the composite graphene slurry is prepared by stirring and ultrasonicating a few-layer graphene powder with a solid content of 3% and a multi-layer graphene powder with a solid content of 5% in a PVA+PVP dispersion system, respectively, wherein the ratio of the graphene slurry prepared from the few-layer graphene powder to the graphene slurry prepared from the multi-layer graphene powder is 3:7.

[0028] In this embodiment, graphene powder is prepared from expandable graphite and pure water by a physical method, wherein the number of layers of the few-layer graphene powder is 2-5 and the particle size (D50) is distributed between 4um-6um, and the number of layers of the multi-layer graphene powder is 5-10 and the particle size (D50) is distributed between 8um-12um.

[0029] In this embodiment, the conductive filler is prepared by mixing and dispersing single-walled carbon nanotube conductive paste and dendritic graphene powder in a mass ratio of 1:0.8.

[0030] In this embodiment, the antioxidant is a mixture of antioxidant 168, antioxidant 1076 and didodecanol thiodipropionate in a weight ratio of 6:3:1.

[0031] In this embodiment, the stabilizer is at least one of sodium stearate and diphenyl phosphite; the flocculant is polyacrylamide A method for preparing a graphene-modified functional masterbatch comprises the following steps: S1: weighing composite graphene slurry and conductive filler by weight into a stirring container, stirring for 30-60 minutes, adding 50-80 parts by weight of polyhydroxy acid water reducer during the stirring process, and drying after being completely mixed to obtain a mixture 1; S2: feeding a base thermoplastic resin into a melting device, and sequentially adding phthalate, a flocculant and a stabilizer weighed in parts by weight during the melting process to mix the mixture to obtain a mixture 2; S3: Putting the mixed material 2, the mixed dry material 1, the antioxidant, the aluminate coupling agent and the talc powder into a granulator in sequence for mixing and granulation, thereby obtaining the graphene-modified functional masterbatch.

[0032] In this embodiment, the granulation particle size in the above step three is 1 mm to 3 mm. Example

[0033] A graphene-modified functional masterbatch consists of the following components by weight: 12 parts of a basic thermoplastic resin, 10 parts of a composite graphene slurry prepared by a physical method, 13 parts of a conductive filler, 0.3 parts of a phthalate, 0.4 parts of an antioxidant, 0.6 parts of a flocculant, 1.2 parts of a stabilizer, 0.6 parts of an aluminate coupling agent, and 1.2 parts of talc.

[0034] In this embodiment, the base thermoplastic resin may be a polyamide resin, a polyethylene resin, or a polypropylene resin.

[0035] In this embodiment, the composite graphene slurry is prepared by stirring and ultrasonicating a few-layer graphene powder with a solid content of 3% and a multi-layer graphene powder with a solid content of 5% in a PVA+PVP dispersion system, respectively, wherein the ratio of the graphene slurry prepared from the few-layer graphene powder to the graphene slurry prepared from the multi-layer graphene powder is 3:7.

[0036] In this embodiment, graphene powder is prepared from expandable graphite and pure water by a physical method, wherein the number of layers of the few-layer graphene powder is 2-5 and the particle size (D50) is distributed between 4um-6um, and the number of layers of the multi-layer graphene powder is 5-10 and the particle size (D50) is distributed between 8um-12um.

[0037] In this embodiment, the conductive filler is prepared by mixing and dispersing single-walled carbon nanotube conductive paste and dendritic graphene powder in a mass ratio of 1:0.6.

[0038] In this embodiment, the antioxidant is a mixture of antioxidant 168, antioxidant 1076 and didodecanol thiodipropionate in a weight ratio of 6:3:1.

[0039] In this embodiment, the stabilizer is at least one of sodium stearate and diphenyl phosphite; the flocculant is polyacrylamide A method for preparing a graphene-modified functional masterbatch comprises the following steps: S1: weighing composite graphene slurry and conductive filler by weight into a stirring container, stirring for 30-60 minutes, adding 50-80 parts by weight of polyhydroxy acid water reducer during the stirring process, and drying after being completely mixed to obtain a mixture 1; S2: feeding a base thermoplastic resin into a melting device, and sequentially adding phthalate, a flocculant and a stabilizer weighed in parts by weight during the melting process to mix the mixture to obtain a mixture 2; S3: Putting the mixed material 2, the mixed dry material 1, the antioxidant, the aluminate coupling agent and the talc powder into a granulator in sequence for mixing and granulation, thereby obtaining the graphene-modified functional masterbatch.

[0040] In this embodiment, the granulation particle size in the above step three is 1 mm to 3 mm. Example

[0041] A graphene-modified functional masterbatch consists of the following components by weight: 10 parts of a basic thermoplastic resin, 12 parts of a composite graphene slurry prepared by a physical method, 12 parts of a conductive filler, 0.2 parts of a phthalate, 0.2 parts of an antioxidant, 0.5 parts of a flocculant, 1 part of a stabilizer, 0.5 parts of an aluminate coupling agent, and 1 part of talc.

[0042] In this embodiment, the base thermoplastic resin may be a polyamide resin, a polyethylene resin, or a polypropylene resin.

[0043] In this embodiment, the composite graphene slurry is prepared by stirring and ultrasonicating a few-layer graphene powder with a solid content of 3% and a multi-layer graphene powder with a solid content of 5% in a PVA+PVP dispersion system, respectively, wherein the ratio of the graphene slurry prepared from the few-layer graphene powder to the graphene slurry prepared from the multi-layer graphene powder is 3:7.

[0044] In this embodiment, graphene powder is prepared from expandable graphite and pure water by a physical method, wherein the number of layers of the few-layer graphene powder is 2-5 and the particle size (D50) is distributed between 4um-6um, and the number of layers of the multi-layer graphene powder is 5-10 and the particle size (D50) is distributed between 8um-12um.

[0045] In this embodiment, the conductive filler is prepared by mixing and dispersing single-walled carbon nanotube conductive paste and dendritic graphene powder in a mass ratio of 1:0.6.

[0046] In this embodiment, the antioxidant is a mixture of antioxidant 168, antioxidant 1076 and didodecanol thiodipropionate in a weight ratio of 6:3:1.

[0047] In this embodiment, the stabilizer is at least one of sodium stearate and diphenyl phosphite; the flocculant is polyacrylamide A method for preparing a graphene-modified functional masterbatch comprises the following steps: S1: weighing composite graphene slurry and conductive filler by weight into a stirring container, stirring for 30-60 minutes, adding 50-80 parts by weight of polyhydroxy acid water reducer during the stirring process, and drying after being completely mixed to obtain a mixture 1; S2: feeding a base thermoplastic resin into a melting device, and sequentially adding phthalate, a flocculant and a stabilizer weighed in parts by weight during the melting process to mix the mixture to obtain a mixture 2; S3: Putting the mixed material 2, the mixed dry material 1, the antioxidant, the aluminate coupling agent and the talc powder into a granulator in sequence for mixing and granulation, thereby obtaining the graphene-modified functional masterbatch.

[0048] In this embodiment, the granulation particle size in the above step three is 1 mm to 3 mm.

[0049] The volume resistivity, surface resistivity, tensile strength and flexural strength of the above Examples 1-4 were tested and compared with the traditional carbon black PA masterbatch. The results are as follows: Volume resistivity Ω·m Surface resistivity Ω·m Tensile strength MPa Flexural strength MPa Traditional carbon black masterbatch (PA) 2×10^3 1×10^5 33 52 Example 1 4.5×10^13 2.9×10^11 43.89 69.16 Example 2 3.6×10^13 2.8×10^11 42.58 68.33 Example 3 3×10^13 2×10^11 41.32 67.58 Example 4 2.2×10^13 1.2×10^11 41.2 66.8 In summary, compared with traditional carbon black masterbatch (PA), the addition of composite graphene slurry prepared by physical method can significantly improve the tensile and bending strength of thermoplastic resin masterbatch by about 33%, and both volume resistivity and surface resistivity are greatly improved, that is, it has better antistatic properties.

[0050] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions only describe the principles of the present invention. The present invention may be subject to various changes and improvements without departing from the spirit and scope of the present invention. These changes and improvements fall within the scope of the present invention. The scope of protection claimed by the present invention is defined by the attached claims and their equivalents.

Claims

1. A graphene-modified functional masterbatch, characterized in that: The masterbatch consists of the following components by weight: 10-18 parts of basic thermoplastic resin, 8-12 parts of composite graphene slurry prepared by a physical method, 12-15 parts of conductive filler, 0.2-0.6 parts of phthalate, 0.2-0.8 parts of antioxidant, 0.5-1 parts of flocculant, 1-2 parts of stabilizer, 0.5-1 parts of aluminate coupling agent and 1-2 parts of talc.

2. The graphene-modified functional masterbatch according to claim 1, characterized in that: The base thermoplastic resin may be a polyamide resin, a polyethylene resin or a polypropylene resin.

3. According to a graphene-modified functional masterbatch according to claim 1, it is characterized in that: The composite graphene slurry is prepared by stirring and ultrasonicating a few-layer graphene powder with a solid content of 3% and a multi-layer graphene powder with a solid content of 5% in a PVA+PVP dispersion system, respectively, wherein the ratio of the graphene slurry prepared from the few-layer graphene powder to the graphene slurry prepared from the multi-layer graphene powder is 3:

7.

4. The graphene-modified functional masterbatch according to claim 3, characterized in that: The graphene powder is prepared from expandable graphite and pure water by a physical method, wherein the number of layers of the few-layer graphene powder is 2-5 and the particle size (D50) is distributed between 4um-6um, and the number of layers of the multi-layer graphene powder is 5-10 and the particle size (D50) is distributed between 8um-12um.

5. According to a graphene-modified functional masterbatch according to claim 1, it is characterized in that: The conductive filler is prepared by compounding and dispersing single-walled carbon nanotube conductive slurry and dendritic graphene powder in a mass ratio of 1:0.6-0.

8.

6. The graphene-modified functional masterbatch according to claim 1, characterized in that: The antioxidant is prepared by mixing antioxidant 168, antioxidant 1076 and didodecanol thiodipropionate in a weight ratio of 6:3:

1.

7. According to a graphene-modified functional masterbatch according to claim 1, it is characterized in that: The stabilizer is at least one of sodium stearate and diphenyl phosphite; and the flocculant is polyacrylamide.

8. A method for preparing a graphene-modified functional masterbatch according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1: weighing composite graphene slurry and conductive filler by weight into a stirring container, stirring for 30-60 minutes, adding 50-80 parts by weight of polyhydroxy acid water reducer during the stirring process, and drying after being completely mixed to obtain a mixture 1; S2: feeding a base thermoplastic resin into a melting device, and sequentially adding phthalate, a flocculant and a stabilizer weighed in parts by weight during the melting process to mix the mixture to obtain a mixture 2; S3: Putting the mixed material 2, the mixed dry material 1, the antioxidant, the aluminate coupling agent and the talc powder into a granulator in sequence for mixing and granulation, thereby obtaining the graphene-modified functional masterbatch.

9. The method for preparing a graphene-modified functional masterbatch according to claim 8, characterized in that: The granulation particle size in step 3 is 1 mm to 3 mm.