CN116218078A - Superconducting polyolefin material - Google Patents

Superconducting polyolefin material Download PDF

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CN116218078A
CN116218078A CN202310102481.6A CN202310102481A CN116218078A CN 116218078 A CN116218078 A CN 116218078A CN 202310102481 A CN202310102481 A CN 202310102481A CN 116218078 A CN116218078 A CN 116218078A
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ionic liquid
polyolefin
area
filled
superconducting
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翁永华
王在华
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Suzhou Haiju Polymer Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
    • Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to a superconducting polyolefin material and a preparation method thereof, wherein the superconducting polyolefin material is prepared from the following raw materials in percentage by weight:

Description

Superconducting polyolefin material
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a superconducting polyolefin material and a preparation method thereof.
Background
Polyolefin such as PP, PE, etc. is an insulating material with volume resistivity of 1×10 16 ～1×10 18 Omega.m, static charge is liable to accumulate during production and use to a pointStatic discharge phenomenon can be generated after a certain degree, daily use of the product is hindered, more serious consequences can cause damage of electronic equipment, even fire disaster is caused, serious potential safety hazard exists, and therefore the application range of polyolefin products is limited. However, the polyolefin such as PP, PE has the advantages of light weight, corrosion resistance, low cost, easy processing and the like, and if the polyolefin material such as PP, PE and the like is modified into a permanent conductive/antistatic material, the application range of the polyolefin is greatly expanded, and even some industries can be subverted.
There are several methods currently under investigation for conductive polyolefins: 1. the surface treatment method refers to conducting treatment on the surface of polyolefin to achieve higher conductivity, including a metal thermal spraying method, a dry plating method, a wet plating method and a conducting coating method, and the polyolefin after the surface treatment can enable charges to leak out rapidly and prevent electromagnetic wave and radio frequency interference (EMI/RFI). The surface treatment method has complex process and high cost, and the surface conductive layer is easy to damage under the action of external force, so that the application of the surface conductive layer is limited to a certain extent; 2. the filler dispersion compounding method is to mix conductive filler into plastic to prepare conductive polyolefin. The conductive filler mainly comprises particles, fibrous carbon, lamellar and the like, wherein lamellar dispersion technology of a disperse phase is a new technology which is widely valued at present; 3. the conductive filler lamination composite method is to laminate polyolefin on two sides of a metal net, a plate, a silk felt and the like serving as an intermediate layer or prepare a layer of conductive resin by a double-layer parallel extrusion method. The other layer is a double layer product of common resin, and the technology is in the development stage at present. Therefore, the first scheme has complex process and is influenced by external force, the third scheme has limitation on the shape of the product, and only a few simple lamellar plates or linear materials can be made, while the second scheme has wider thought, but the current research is less, and the effect is not very good because the conductive filler is mainly simply added.
Thus, there is still a need for polyolefin materials having excellent conductive effects.
Disclosure of Invention
In order to solve the problems, the invention introduces a novel conductive system based on the second scheme, breaks through the traditional conductive mechanism and realizes the excellent conductive effect of polyolefin. More specifically, the invention prepares the super conductive polymer material with ultralow surface resistivity by introducing a proper conductive agent into polyolefin, which has good conductivity on one hand and good processability and chemical corrosion resistance on the other hand.
In order to achieve the above purpose, the technical scheme of the invention is that firstly, the silicon dioxide nanotube is filled with the ionic liquid, and then the polyolefin, the silicon dioxide nanotube filled with the ionic liquid, the high-temperature ionic liquid, the compatilizer, the lubricant and other auxiliary agents are extruded to form granules, so that the obtained polyolefin material has excellent conductive effect, excellent processability and chemical corrosion resistance, and excellent physical and mechanical properties and apparent properties.
Therefore, in one aspect, the invention provides a superconducting polyolefin material, which is prepared from the following raw materials in percentage by weight:
Figure BDA0004073445210000021
more preferably, the invention provides a superconducting polyolefin material which is prepared from the following raw materials in percentage by weight:
Figure BDA0004073445210000031
more preferably, the invention provides a superconducting polyolefin material which is prepared from the following raw materials in percentage by weight:
Figure BDA0004073445210000032
as used herein, the polyolefin may be any suitable polyolefin material. Preferably, the polyolefin is a linear polymer. More preferably, the polyolefin comprises polypropylene, polyethylene or a mixture thereof.
More specifically, the silica nanotubes have a length of 0.1 to 10 micrometers, an inner diameter of 20 to 100 nanometers, and are internally filled with an ionic liquid.
More specifically, the length of the silica nanotubes may be any value in the range of 0.1-10 microns, for example, the length of the silica nanotubes may be 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 microns, or a range between any of the foregoing values.
More specifically, the inner diameter of the silica nanotubes may be any value in the range of 20-100 nanometers, for example, the inner diameter of the silica nanotubes may be 20, 30, 40, 50, 60, 70, 80, 90, 100 nanometers, or any range between the foregoing values.
More specifically, the silica nanotubes filled with the ionic liquid were prepared as follows:
1) The silica is packed into a chromatographic column,
2) Heating the selected ionic liquid to 100 ℃ and pouring the ionic liquid into the silica chromatographic column in the step 1),
3) The ionic liquid is quickly permeated and filled into the silica chromatographic column through the booster pump,
4) The ionic liquid is kept to be immersed in the silicon dioxide for 20 to 30min,
5) And taking out the silicon dioxide filled with the ionic liquid, and drying to obtain the silicon dioxide nanotube filled with the ionic liquid.
More specifically, the ionic liquid is an ionic liquid having a viscosity of 50-150cP, which comprises CF 3 COO - 、CF 3 SO 3 - Sum (CF) 3 SO 2 )N - One or more of the following.
More specifically, the high temperature ionic liquid is a K-series ionic liquid. Preferably, the K-series ionic liquid may include, but is not limited to, KCI, KOH, or mixtures thereof.
More specifically, the compatibilizing agent includes, but is not limited to, maleic anhydride grafted PP with a grafting ratio of 80% or more.
As used herein, the lubricant is generally not limited and may be selected from any suitable lubricant known in the art. More specifically, the lubricant comprises polytetrafluoroethylene,
as used herein, a heat stabilizer is generally not limited and may be selected from any suitable heat stabilizer known in the art. More specifically, the heat stabilizer is a heat stabilizer DSTP,
as used herein, antioxidants are generally not limited and may be selected from any suitable antioxidants well known in the art. More specifically, the antioxidant is a compounded antioxidant consisting of 0.1-1.0 weight percent of antioxidant 1010 and 0.1-0.5 weight percent of antioxidant 168 based on the total weight of the polyolefin material.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1:
the present example provides a superconducting polyolefin material prepared as follows:
according to weight percentage, polypropylene 80%, silicon dioxide nanotube (filled with ionic liquid) 5%, high temperature ionic liquid 3%, maleic anhydride grafted PP (grafting rate is more than or equal to 80%) 6%, polytetrafluoroethylene 5%, heat stabilizer DSTP 0.4%, antioxidant 1010 0.4%, antioxidant 168.2% are dry mixed in a high-speed mixer for 3-5 minutes, and then are melt extruded in a twin-screw extruder and granulated, the process is as follows: 180-190 ℃ in the first area, 200-210 ℃ in the second area, 200-210 ℃ in the third area, 210-215 ℃ in the fourth area, 210-215 ℃ in the fifth area, 210-215 ℃ in the sixth area, 210-215 ℃ in the seventh area, 215-225 ℃ in the eighth area, 215-225 ℃ in the ninth area, 215-225 ℃ in the tenth area, and 215-225 ℃; the residence time is 1-2 minutes and the pressure is 12-18MPa.
Example 2
The present example provides a superconducting polyolefin material prepared as follows:
according to weight percentage, 75% of polypropylene, 6% of silicon dioxide nano tube (filled with ionic liquid), 3% of high temperature ionic liquid, 9% of maleic anhydride grafted PP (grafting rate is more than or equal to 80%), 6% of polytetrafluoroethylene, 0.4% of heat stabilizer DSTP, 0.4% of antioxidant 1010 and 168.2% of antioxidant are dry mixed in a high-speed mixer for 3-5 minutes, and then are subjected to melt extrusion in a double-screw extruder and pelleting, wherein the process comprises the following steps: 180-190 ℃ in the first area, 200-210 ℃ in the second area, 200-210 ℃ in the third area, 210-215 ℃ in the fourth area, 210-215 ℃ in the fifth area, 210-215 ℃ in the sixth area, 210-215 ℃ in the seventh area, 215-225 ℃ in the eighth area, 215-225 ℃ in the ninth area, 215-225 ℃ in the tenth area, and 215-225 ℃; the residence time is 1-2 minutes and the pressure is 12-18MPa.
Example 3
The present example provides a superconducting polyolefin material prepared as follows:
according to weight percentage, 68% of polypropylene, 8% of silicon dioxide nano tube (filled with ionic liquid), 4% of high temperature ionic liquid, 11% of maleic anhydride grafted PP (grafting rate is more than or equal to 80%), 8% of polytetrafluoroethylene, 0.2% of heat stabilizer DSTP, 0.4% of antioxidant 1010 and 168.4% of antioxidant are dry mixed in a high-speed mixer for 3-5 minutes, and then are melt extruded in a double screw extruder and granulated, and the process comprises the following steps: 180-190 ℃ in the first area, 200-210 ℃ in the second area, 200-210 ℃ in the third area, 210-215 ℃ in the fourth area, 210-215 ℃ in the fifth area, 210-215 ℃ in the sixth area, 210-215 ℃ in the seventh area, 215-225 ℃ in the eighth area, 215-225 ℃ in the ninth area, 215-225 ℃ in the tenth area, and 215-225 ℃; the residence time is 1-2 minutes and the pressure is 12-18MPa.
Example 4
The present example provides a superconducting polyolefin material prepared as follows:
according to weight percentage, polypropylene 60%, silicon dioxide nanotube (filled with ionic liquid) 10%, high temperature ionic liquid 5%, maleic anhydride grafted PP (grafting rate is more than or equal to 80%) 14%, polytetrafluoroethylene 10%, heat stabilizer DSTP 0.4%, antioxidant 1010 0.3% and antioxidant 168.3% are dry mixed in a high-speed mixer for 3-5 minutes, and then are melt extruded in a double screw extruder and granulated, and the process comprises the following steps: 180-190 ℃ in the first area, 200-210 ℃ in the second area, 200-210 ℃ in the third area, 210-215 ℃ in the fourth area, 210-215 ℃ in the fifth area, 210-215 ℃ in the sixth area, 210-215 ℃ in the seventh area, 215-225 ℃ in the eighth area, 215-225 ℃ in the ninth area, 215-225 ℃ in the tenth area, and 215-225 ℃; the residence time is 1-2 minutes and the pressure is 12-18MPa.
Comparative example 1 (with reference to example 3)
This comparative example provides a polyolefin material prepared as follows:
68% of polypropylene, 8% of ionic liquid, 4% of high-temperature ionic liquid, 11% of maleic anhydride grafted PP (grafting rate is more than or equal to 80%), 8% of polytetrafluoroethylene, 0.2% of heat stabilizer DSTP, 0.4% of antioxidant 1010 and 168.4% of antioxidant are dry mixed in a high-speed mixer for 3-5 minutes, and then are melt extruded in a double-screw extruder for granulation, wherein the process comprises the following steps: 180-190 ℃ in the first area, 200-210 ℃ in the second area, 200-210 ℃ in the third area, 210-215 ℃ in the fourth area, 210-215 ℃ in the fifth area, 210-215 ℃ in the sixth area, 210-215 ℃ in the seventh area, 215-225 ℃ in the eighth area, 215-225 ℃ in the ninth area, 215-225 ℃ in the tenth area, and 215-225 ℃; the residence time is 1-2 minutes and the pressure is 12-18MPa.
Performance evaluation mode and implementation standard:
the granulated particle material is dried in a blast oven at 60 ℃ for 2 to 3 hours in advance, and then the dried particle material is subjected to injection molding sample preparation on an injection molding machine.
The tensile property test was carried out according to ISO 527-2, the sample size was 150X 10X 4mm, and the tensile speed was 50mm/min; bending performance test was conducted according to ISO 178, the sample size was 80X 10X 4mm, the bending speed was 2mm/min, and the span was 64mm; the impact strength of the simply supported beam is carried out according to ISO 179, the size of a sample is 80 multiplied by 6 multiplied by 4mm, and the depth of a notch is one third of the thickness of the sample; the density was determined in accordance with ISO 1183 and the sample size was 10X 4mm.
The formulations of the above examples and the results of the performance tests are shown in the following table:
table 1: formulation and Material Property Table for examples 1-4 and comparative example 1
Figure BDA0004073445210000071
Figure BDA0004073445210000081
As can be seen from examples 1-4 of table 1, the conductive polyolefin is composed of polyolefin and a high-low temperature ionic liquid conductive system, the high-low temperature ionic liquid is composed of silica nanotubes (filled with ionic liquid) and a high-temperature ionic liquid, as the content of the ionic liquid conductive system increases, the surface resistance decreases, the conductive effect increases, and meanwhile, the mechanical property of the material, especially the impact property, is greatly improved by more than 1 time, the flexural modulus is improved by nearly 50%, and in addition, the appearance of the material is very good, and no warpage, precipitation and flow mark are caused; when the conductive system reaches 12%, the conductivity, mechanical property and appearance of the material reach comprehensive best, and when the conductive system is continuously added, the related performance is not improved, but partial conductive agent is separated out due to supersaturation of the conductive system; as can be seen from example 3 and comparative example 1 in Table 1, the conventional method only uses ionic liquid, which has the advantages of general conductive effect, 2000 Ω surface resistance and poor mechanical properties, and the conductive system of the present invention has the advantages of generally improved mechanical properties, especially impact properties, improved by more than 1 time, improved other mechanical properties by about 50%, and excellent appearance. The silicon dioxide nano tube filled with the ionic liquid is introduced into the material, and is compounded and used by the high-temperature ionic liquid, so that the ionic liquid at normal temperature is uniformly distributed to form a linear state by the action of the compatilizer and the lubricant, and is uniformly distributed to form a point block state by combining the high-temperature ionic liquid, a compact conductive network is formed by combining the point-line state, and the conductive efficiency is greatly improved.
In the description of the specification, reference to the term "one embodiment," "a particular embodiment," "an example," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or by similar arrangements, by those skilled in the art, without departing from the scope of the invention or beyond the scope of the appended claims.

Claims (10)

1. A superconducting polyolefin material, characterized by: the material is prepared from the following raw materials in percentage by weight:
Figure FDA0004073445200000011
2. the superconducting polyolefin material of claim 1, wherein: the material is prepared from the following raw materials in percentage by weight:
Figure FDA0004073445200000012
3. the superconducting polyolefin material of claim 1, wherein: the material is prepared from the following raw materials in percentage by weight:
Figure FDA0004073445200000013
Figure FDA0004073445200000021
4. a polyolefin according to any of claims 1 to 3, characterized in that: the polyolefin is a linear polymer which is a polymer,
for example, the polyolefin comprises polypropylene, polyethylene, or a mixture thereof.
5. A polyolefin according to any of claims 1 to 3, characterized in that: the length of the silica nanotube is 0.1-10 micrometers, the inner diameter is 20-100 nanometers, and the interior is filled with ionic liquid.
6. The polyolefin according to claim 5, wherein: the silica nanotubes filled with ionic liquid were prepared as follows:
1) The silica is packed into a chromatographic column,
2) Heating the selected ionic liquid to 100 ℃ and pouring the ionic liquid into the silica chromatographic column in the step 1),
3) The ionic liquid is quickly permeated and filled into the silica chromatographic column through the booster pump,
4) The ionic liquid is kept to be immersed in the silicon dioxide for 20 to 30min,
5) And taking out the silicon dioxide filled with the ionic liquid, and drying to obtain the silicon dioxide nanotube filled with the ionic liquid.
7. The polyolefin according to claim 6, wherein: the ionic liquid is an ionic liquid with viscosity of 50-150cP and comprises CF 3 COO - 、CF 3 SO 3 - Sum (CF) 3 SO 2 )N - One or more of the following.
8. A polyolefin according to any of claims 1 to 3, characterized in that: the high-temperature ionic liquid is K-series ionic liquid,
for example, the K-series ionic liquid includes KCI, KOH, or a mixture thereof.
9. A polyolefin according to any of claims 1 to 3, characterized in that: the compatilizer comprises maleic anhydride grafted PP, and the grafting rate is more than or equal to 80 percent.
10. A polyolefin according to any of claims 1 to 3, characterized in that: the lubricant comprises Polytetrafluoroethylene (PTFE),
preferably, the heat stabilizer is a heat stabilizer DSTP,
preferably, the antioxidants include 0.1-1.0 weight percent antioxidant 1010 and 0.1-0.5 weight percent antioxidant 168.
CN202310102481.6A 2023-02-13 2023-02-13 Superconducting polyolefin material Pending CN116218078A (en)

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