CN112175300A - Carbon nanotube master batch and preparation method and application thereof - Google Patents

Carbon nanotube master batch and preparation method and application thereof Download PDF

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CN112175300A
CN112175300A CN202010965070.6A CN202010965070A CN112175300A CN 112175300 A CN112175300 A CN 112175300A CN 202010965070 A CN202010965070 A CN 202010965070A CN 112175300 A CN112175300 A CN 112175300A
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master batch
carbon nanotube
conductive
filler
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卢朝亮
叶南飚
黄险波
杨波
吴亦建
吴志强
苏娟霞
罗忠富
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Kingfa Science and Technology Co Ltd
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Priority to PCT/CN2021/073536 priority patent/WO2022052408A1/en
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Abstract

The invention discloses a carbon nanotube master batch which comprises the following components in parts by weight: 50-80 parts of PP resin, 10-40 parts of filler, 3-10 parts of MWCNT and 0.1-3 parts of auxiliary agent; the MWCNT is a multi-walled carbon nanotube, and the filler is at least one of talcum powder, calcium carbonate, barium sulfate and glass fiber. The carbon nanotube master batch can be used for preparing the MWCNT master batch with high dispersion degree under the condition of common double-screw extrusion by controlling various components and content, and the problem that the MWCNT structure is easily damaged because professional equipment is used for banburying in the conventional master batch preparation process is solved. Meanwhile, the invention also discloses a preparation method and application of the carbon nano tube master batch.

Description

Carbon nanotube master batch and preparation method and application thereof
Technical Field
The invention relates to the field of modification of high polymer materials, in particular to a carbon nano tube master batch and a preparation method and application thereof.
Background
The polypropylene (PP) is used as a general plastic with high cost performance, has excellent mechanical properties after toughening and modification, is simple and convenient to form and process, and is widely applied to household appliances and automobile products.
In the future automobile automatic driving technology, a great amount of millimeter wave radars are used in an automatic cruise (ACC), an anti-collision system (CA), a lane change auxiliary system and the like, and with the development of the technology, a 77GHz millimeter wave radar is generally industrialized in the industry and replaces a 24GHz millimeter wave radar to become a mainstream of the application of the automobile millimeter wave radar, and under the condition, the anti-interference of the radar is particularly important.
Because of the problem that multi-walled carbon nanotubes (MWCNTs) are small in density and difficult to disperse, when the MWCNTs are used for preparing the conductive polypropylene composition, the MWCNTs are difficult to disperse and easy to cause dust pollution in the production process, most of the MWCNT master batches sold in the market at present are produced by adopting an internal mixing high-shear method, professional equipment and processes and professional formula design are needed, the formula design freedom degree is low and complicated, and therefore the preparation method of the MWCNT master batches, which is efficient, convenient and cost-saving, is needed to improve the dispersibility of the MWCNTs in matrix resin and reduce the dust pollution in the production process. Meanwhile, polypropylene is less prone to realize conductivity compared with other polar resins, so that relatively few reports on conductive polypropylene products in the market are provided at present, and the conventional scheme for realizing material conductivity has the problems of extremely high additive amount, unstable production and material conductivity fluctuation in a polypropylene system, so that a simple and feasible method for preparing a conductive polypropylene material is needed to be developed in the field, and the method is suitable for automobile interior and exterior parts with electromagnetic shielding requirements.
Disclosure of Invention
Based on the above, the present invention aims to overcome the disadvantages of the prior art and provide a carbon nanotube master batch.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: the carbon nanotube master batch comprises the following components in parts by weight: 50-80 parts of PP resin, 10-40 parts of filler, 3-10 parts of MWCNT and 0.1-3 parts of auxiliary agent; the filler is at least one of talcum powder, calcium carbonate, barium sulfate and glass fiber.
Preferably, the carbon nanotube master batch comprises the following components in parts by weight: 50-80 parts of PP resin, 20-30 parts of filler, 5-8 parts of MWCNT and 0.1-3 parts of auxiliary agent.
Preferably, at least one of the following (a) to (c):
(a) the PP resin is at least one of homo-polypropylene and co-polypropylene, and the melt mass flow rate of the PP resin at 230 ℃ and under a load of 2.16Kg is 1-100 g/10 min;
(b) the MWCNT is a multi-wall carbon nano-tube, the tube diameter of the MWCNT is 8-60nm, and the length of the MWCNT is 2-100 mu m;
(c) the auxiliary agent is one or more of an antioxidant, a light stabilizer and a lubricant.
Meanwhile, the invention also provides a preparation method of the carbon nano tube master batch, which comprises the following steps: uniformly mixing PP resin, MWCNT, filler and an auxiliary agent, adding the mixture into a double-screw extruder, and carrying out melt mixing and extrusion granulation to obtain carbon nanotube master batches; wherein the temperature of the melt mixing is 200-210 ℃, and the screw rotating speed of the double-screw extruder is 350-450 r/min.
The invention also provides the application of the carbon nano tube master batch in conductive polypropylene materials.
In addition, the invention also provides a conductive polypropylene material containing the carbon nano tube master batch, which comprises the following components in parts by weight: 20-70 parts of PP resin, 0-30 parts of toughening agent, 0-40 parts of filler, 10-50 parts of carbon nanotube master batch, 10-50 parts of conductive carbon black master batch and 0.1-3 parts of auxiliary agent.
Preferably, in the conductive carbon black master batch, the weight percentage content of the conductive carbon black is more than or equal to 40%, and the oil absorption value of the conductive carbon black is more than or equal to 120m3100g of; the conductive carbon black has an oil absorption value measured in accordance with ASTM D3493-2016.
Preferably, the conductive polypropylene material comprises the following components in parts by weight: 20-70 parts of PP resin, 0-30 parts of toughening agent, 0-40 parts of filler, 20-40 parts of carbon nanotube master batch, 15-35 parts of conductive carbon black master batch and 0.1-3 parts of auxiliary agent.
Preferably, at least one of the following (1) to (4):
(1) the PP resin is at least one of homo-polypropylene and co-polypropylene, and the melt mass flow rate of the PP resin at 230 ℃ and under a load of 2.16Kg is 1-100 g/10 min;
(2) the toughening agent is one or more of POE plastic, hydrogenated styrene-butadiene block copolymer (SEBS) and Ethylene Propylene Diene Monomer (EPDM);
(3) the filler is one or more of talcum powder, calcium carbonate, barium sulfate and glass fiber;
(4) the auxiliary agent is one or more of an antioxidant, a light stabilizer and a lubricant.
More preferably, at least one of the following (a) to (b):
(a) the melt mass flow rate of the toughening agent at 190 ℃ under the load of 2.16Kg is 0.1-20g/10 min;
(b) the particle fineness of the filler is 1000-5000 meshes.
Preferably, the antioxidant is hindered phenol and/or phosphite antioxidant, and specifically can be one or a mixture of two or more of 1010, 1076, 3114, 168 and PEP-36;
the light stabilizer is hindered amine light stabilizer, and specifically can be one or a mixture of two or more of UV-3808PP5, LA-402XP and LA-402 AF;
the lubricant is one or a mixture of two or more of silicones, esters, amides, polyethylenes, stearic acids, fatty acids and esters.
Further, the invention also provides a preparation method of the conductive polypropylene material, which comprises the following steps: uniformly mixing PP resin, a toughening agent, a filler, carbon nanotube master batches, conductive carbon black master batches and an auxiliary agent, adding the mixture into a double-screw extruder, and carrying out melt mixing, extrusion and granulation to obtain a conductive polypropylene material; wherein the melting and mixing temperature is 200-210 ℃, and the screw rotating speed of the double-screw extruder is 350-450 r/min.
In addition, the invention also discloses application of the conductive polypropylene material in automobile interior and exterior parts with electromagnetic shielding requirements.
Compared with the prior art, the invention has the beneficial effects that:
1) the carbon nanotube master batch realizes the preparation of the MWCNT master batch with high dispersion degree under the condition of common double-screw extrusion by controlling various components and content, gets rid of the problem that the MWCNT master batch is easy to damage due to the fact that professional equipment is required to be used for banburying in the conventional master batch preparation process, has higher formula design freedom degree and is simple and convenient to operate, and thus is not limited by the limitation of the MWCNT master batch product on the market.
2) The production method of the MWCNT master batch is simple and convenient to implement, has cost advantage and high design freedom.
3) Compared with the conventional polypropylene conductive scheme, the production method of the prepared conductive polypropylene composition is convenient to realize, the content of the conductive filler required to be added is lower, the material conductivity is higher, and the conductive polypropylene composition has the advantages of simplicity, convenience, low cost and higher conductivity.
4) The prepared conductive polypropylene composition has very high conductivity, and is suitable for being used as an EMI material, and is used for automobile interior and exterior trimming parts with EMI characteristic requirements and other application occasions with EMI requirements.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. The following examples are merely exemplary of the present invention, and the scope of the present invention is not limited thereto. In the following examples and comparative examples, the conductivity test methods were: the sheet resistance of the material was tested according to ASTM D-4496 and D-257; the test standard for impact strength is ISO 527; the flexural modulus test is expressed as ISO 178.
The main representative materials used in the examples and comparative examples are as follows:
PP resin: the melt mass flow rate of the copolymerized polypropylene at 230 ℃ and under the load of 2.16Kg is 40g/10min, and the name of the petrochemical polypropylene is rich;
MWCNT: the pipe diameter is 8-15nm, the length is 10-70um, and the chemical formula of LG is adopted;
filler 1 (talc): particle fineness of 3000 mesh, north sea group;
filler 2 (talc): particle size of 325 mesh, North sea group
Toughener 1 (POE): melt mass flow rate at 190 ℃ under 2.16Kg load is 1.2g/10min, Dow chemical;
toughener 2 (POE): melt mass flow rate at 190 ℃ under 2.16Kg load is 30g/10min, Dow chemical;
conductive carbon black master batch 1: the weight percentage content of the conductive carbon black is 50 percent, and the oil absorption value of the conductive carbon black is 150m3100g [ measurement standard ASTM D3493-2016 ], Ficus microcarpa, Taiwan;
conductive carbon black master batch 2: the weight percentage of the conductive carbon black is 50 percent, and the oil absorption value of the conductive carbon black is 110m3100g [ measurement standard ASTM D3493-2016 ], Ficus microcarpa, Taiwan;
auxiliary agents (all obtained on the market):
lubricant (Zinc stearate)
Antioxidant (1010/168)
Light stabilizer (UV-3808)
The preparation method of the carbon nano tube master batch comprises the following steps:
uniformly mixing PP resin, MWCNT, filler and an auxiliary agent, adding the mixture into a double-screw extruder, carrying out melt mixing at the temperature of 200-210 ℃ and the rotating speed of 350-450 rpm, and carrying out extrusion granulation to obtain the carbon nanotube master batch.
The preparation method of the conductive polypropylene material comprises the following steps:
uniformly mixing PP resin, a toughening agent, a mineral filler, carbon nanotube master batches, conductive carbon black master batches and an auxiliary agent, adding the mixture into a double-screw extruder, carrying out melt mixing at the temperature of 200-210 ℃ and the screw rotating speed of 350-450 rpm, and carrying out extrusion granulation to obtain the conductive polypropylene material.
In the present application, examples 1 to 11 and comparative examples 1 to 5 were set, and the content of each component of the carbon nanotube master batch 1# to 5# is shown in table 1; the contents and properties of the components of the conductive polypropylene materials in examples 1-11 are shown in Table 2; the contents and properties of the components of the conductive polypropylene materials in comparative examples 1 to 5 are shown in Table 3.
TABLE 1 content of each component of carbon nanotube master batch 1# -5 #
Figure BDA0002679771870000051
TABLE 2 contents and properties of the components of the conductive polypropylene materials in examples 1 to 11
Figure BDA0002679771870000052
Figure BDA0002679771870000061
TABLE 3 content of each component and Properties of the conductive Polypropylene materials in comparative examples 1 to 5
Item Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
PP resin 50 50 50 30
Talcum powder 15
POE 10
Conductive carbon black master batch 25 25 35
MWCNT 2
Carbon nanotube master batch 1# 25
Carbon nanotube master batch 5# 20
Antioxidant agent 0.4 0.4 0.4 0.4
Light stabilizers 0.4 0.4 0.4 0.4
Zinc stearate 0.3 0.3 0.3 0.3
Surface resistance (omega/sq) ＞1.0E+12 5.62E+05 4.81E+06 4.75E+08
Impact Strength (KJ/m)2) 45.78 34.26 45.12 28.54
Flexural modulus (MPa) 1040 1126 1158 1246
As can be seen from Table 2, the results of the conductivity tests on the conductive polypropylene materials obtained in examples 1 to 11 of the present invention are all 104-102The omega/sq level shows that the scheme of compounding the self-made MWCNT master batch and the conductive carbon black master batch in the patent can reduce the addition of the total conductive filler in the system to a great extent and achieve very good material conductivity.
Comparing examples 2 to 5, it can be seen that 20 to 40 parts of the carbon nanotube master batch and 15 to 35 parts of the conductive carbon black master batch in examples 3 and 4, 10 to 50 parts of the carbon nanotube master batch and 10 to 50 parts of the conductive carbon black master batch in examples 2 and 5, the conductivity, impact strength and flexural modulus in examples 3 and 4 are superior to those of examples 2 and 5, and meanwhile, the final product can achieve good conductivity due to the large amount of the MWCNT master batch in example 2, but the product cost is much higher than those of examples 3 and 4; in example 5, the ratio of the conductive carbon black is very high, and although the conductivity of the product is high, problems tend to occur in the production process.
Comparing examples 3 and 6 to 8, it can be seen that the carbon nanotube master batch in examples 3 and 6 contains 20 to 30 parts of filler and 5 to 8 parts of MWCNT; in the carbon nanotube master batch in examples 7 and 8, 10 to 40 parts of filler and 3 to 10 parts of MWCNT are added; examples 3 and 6 are superior to examples 7 and 8 in impact strength and flexural modulus, examples 3 and 6 are superior to example 8 in conductivity, and example 7 is also superior in conductivity, but does not have a good practical productivity because: the carbon nanotube master batch 3# contains very high talcum powder and MWCNT ratio, so that the production of the master batch is not stable, and the improvement of the conductivity of the material is not facilitated.
Comparing example 1 with comparative examples 1 to 3, it can be seen that comparative examples 1 and 3 only contain at least one of the conductive carbon black master batch and the carbon nanotube master batch, and comparative example 2 directly adopts the MWCNT powder and the conductive carbon black master batch to compound (25 parts of MWCNT master batch 1# contains 2 parts of MWCNT as the active ingredient), and the conductivity, impact property and flexural modulus in comparative examples 1 to 3 are all inferior to those in example 1.
Comparing comparative example 4 with example 6, it can be seen that the carbon nanotube master batch of comparative example 4 does not contain filler, and the conductivity, impact property, and flexural modulus are inferior to those of example 6.
Comparing example 3 with example 9, it can be seen that the fineness of the filler particles in example 9 is less than 1000 mesh, and the conductivity, impact performance and flexural modulus are all inferior to those of example 3; comparing example 3 with example 10, it can be seen that the melt mass flow in example 10The rate is more than 20g/10min, and the conductivity, impact property and flexural modulus are all inferior to those of example 3; comparing example 3 with example 11, it can be seen that the conductive carbon black masterbatch of example 11 has an oil absorption value of less than 120m3100g, the conductivity, impact performance and flexural modulus are all inferior to those of example 3.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (11)

1. The carbon nanotube master batch is characterized by comprising the following components in parts by weight: 50-80 parts of PP resin, 10-40 parts of filler, 3-10 parts of MWCNT and 0.1-3 parts of auxiliary agent; the MWCNT is a multi-walled carbon nanotube, and the filler is at least one of talcum powder, calcium carbonate, barium sulfate and glass fiber.
2. The carbon nanotube master batch of claim 1, comprising the following components in parts by weight: 50-80 parts of PP resin, 20-30 parts of filler, 5-8 parts of MWCNT and 0.1-3 parts of auxiliary agent.
3. The carbon nanotube master batch according to claim 1 or 2, wherein at least one of the following (a) to (c):
(a) the PP resin is at least one of homo-polypropylene and co-polypropylene, and the melt mass flow rate of the PP resin at 230 ℃ and under a load of 2.16Kg is 1-100 g/10 min;
(b) the MWCNT has a tube diameter of 8-60nm and a length of 2-100 μm;
(c) the auxiliary agent is one or more of an antioxidant, a light stabilizer and a lubricant.
4. The method for preparing the carbon nanotube master batch according to any one of claims 1 to 3, wherein the method comprises the following steps: uniformly mixing PP resin, MWCNT, filler and an auxiliary agent, adding the mixture into a double-screw extruder, and carrying out melt mixing and extrusion granulation to obtain carbon nanotube master batches; wherein the temperature of the melt mixing is 200-210 ℃, and the screw rotating speed of the double-screw extruder is 350-450 r/min.
5. A conductive polypropylene material containing the carbon nanotube master batch as defined in any one of claims 1 to 3, which is characterized by comprising the following components in parts by weight: 20-70 parts of PP resin, 0-30 parts of toughening agent, 0-40 parts of filler, 10-50 parts of carbon nanotube master batch, 10-50 parts of conductive carbon black master batch and 0.1-3 parts of auxiliary agent.
6. The conductive polypropylene material of claim 5, wherein the conductive carbon black masterbatch contains at least 40 wt% of conductive carbon black, and the conductive carbon black has an oil absorption value of at least 120m3100g of; the conductive carbon black has an oil absorption value measured in accordance with ASTM D3493-2016.
7. The conductive polypropylene material of claim 5, comprising the following components in parts by weight: 20-70 parts of PP resin, 0-30 parts of toughening agent, 0-40 parts of filler, 20-40 parts of carbon nanotube master batch, 15-35 parts of conductive carbon black master batch and 0.1-3 parts of auxiliary agent.
8. The conductive polypropylene material according to claim 5, wherein at least one of the following (1) to (4):
(1) the PP resin is at least one of homo-polypropylene and co-polypropylene, and the melt mass flow rate of the PP resin at 230 ℃ and under a load of 2.16Kg is 1-100 g/10 min;
(2) the toughening agent is one or more of POE plastic, hydrogenated styrene-butadiene block copolymer and ethylene propylene diene monomer;
(3) the filler is one or more of talcum powder, calcium carbonate, barium sulfate and glass fiber;
(4) the auxiliary agent is one or more of an antioxidant, a light stabilizer and a lubricant.
9. The conductive polypropylene material according to claim 8, wherein at least one of the following (a) to (b):
(a) the melt mass flow rate of the toughening agent at 190 ℃ under the load of 2.16Kg is 0.1-20g/10 min;
(b) the particle fineness of the filler is 1000-5000 meshes.
10. The method for preparing the conductive polypropylene material according to any one of claims 6 to 9, wherein the method comprises the following steps: uniformly mixing PP resin, a toughening agent, a filler, carbon nanotube master batches, conductive carbon black master batches and an auxiliary agent, adding the mixture into a double-screw extruder, and carrying out melt mixing, extrusion and granulation to obtain a conductive polypropylene material; wherein the melting and mixing temperature is 200-210 ℃, and the screw rotating speed of the double-screw extruder is 350-450 r/min.
11. Use of the conductive polypropylene material according to any one of claims 6 to 9 in automotive interior and exterior parts requiring electromagnetic shielding.
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