CN111234347B - Method for preparing conductive thermoplastic elastomer by combining prefabricated master batch with phase structure regulation and control - Google Patents
Method for preparing conductive thermoplastic elastomer by combining prefabricated master batch with phase structure regulation and control Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- 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
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- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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Abstract
The invention discloses a method for preparing a conductive thermoplastic elastomer by combining prefabricated master batch and phase structure regulation, which can be used in occasions with characteristics by reducing the using amount of conductive fillers and obviously improving the conductivity of a polymer composite material, thereby improving the application range of the conductive thermoplastic elastomer. The invention discloses a method for preparing a conductive thermoplastic elastomer by combining prefabricated master batch and phase structure regulation, which comprises the following steps of: firstly, evenly mixing polyolefin resin, a conductive material and an auxiliary agent to prepare a mixture; secondly, uniformly blending the mixture to prepare a master batch; thirdly, uniformly blending the master batch and the thermoplastic elastomer to prepare the conductive thermoplastic elastomer; or mixing the thermoplastic elastomer, the conductive material and the auxiliary agent uniformly to prepare a mixture; secondly, uniformly blending the mixture to prepare a master batch; and thirdly, uniformly blending the master batch and the polyolefin resin to obtain the conductive thermoplastic elastomer.
Description
Technical Field
The invention relates to a preparation method of a conductive thermoplastic elastomer, in particular to a method for preparing the conductive thermoplastic elastomer by combining a prefabricated master batch and phase structure regulation and control.
Background
Materials can be classified by electrical properties into insulators, semiconductors, conductors, and superconductors. The common varieties in polymer materials such as Polyethylene (PE), polypropylene (PP), ethylene propylene diene monomer, dimethyl siloxane rubber and styrene butadiene thermoplastic elastomer are typical insulators, and the electrical insulation performance can be represented by electrical conductivity (10)-12～10-16S·m-1) Or volume resistivity (10)12～1016Ω · m) is represented; polymers such as polyaniline, polyacetylene and polyphenylene sulfide are typical conductors, and the conductivity of the conductors is 102～107S·m-1Or a volume resistivity of 10-7～10-2Omega.m. The conductive polymer material is a polymer material with a conductive function, and can be divided into a structural conductive polymer material and a composite conductive polymer material according to the difference of structures. The structural conductive polymer material refers to a polymer material with a polymer structure or a polymer material with a conductive function after being doped, such as polyaniline, polyacetylene, polyphenylene sulfide and other polymers, and the application of the material is limited due to the defects of high cost, poor stability, difficult molding and processing, poor mechanical properties and the like; the composite conductive polymer material is prepared by filling, compounding, surface compounding or laminating and compounding common polymer materials such as polyethylene, polypropylene, polyvinyl chloride and the like and various conductive substances such as silver, conductive carbon black, carbon fiber and the likeTo obtain the product. The conductivity of the conductive polymer material prepared by the latter is generally 10-4～102S·m-1Or a volume resistivity of 10-2～104Omega.m, the conductive polymer material has the characteristics of low cost, simple preparation method, adjustable conductivity, and wide application in many fields, and can utilize the traditional processing methods of general polymer materials, such as injection molding, extrusion molding, blow molding, lamination molding, and the like.
The polyolefin resin has the advantages of excellent electrical insulation performance, good processing performance, excellent mechanical property, good chemical resistance, low price, recycling and the like, and the most important varieties in the polyolefin are Polyethylene (PE) and polypropylene (PP). The polyolefin material has high melting point, high electric breakdown strength and high volume resistivity, and can meet the long-term application requirements of wires and cables at high temperature. Homo-polypropylene (PPH) in polypropylene has a very regular structure, lateral methyl groups are regularly arranged on the same side of a macromolecular main chain, and the polypropylene is easy to crystallize; PPH usually forms alpha crystal when being cooled from a melt, the melting point of a crystal region is about 167 ℃, and the product has good high temperature resistance, high rigidity and high strength; the PPH has high crystallinity which can reach 50 percent or more, so that the PPH has relatively common impact resistance, larger brittleness and particularly extremely poor low-temperature toughness. Among polyethylene, High Density Polyethylene (HDPE) is generally produced by a Ziegler-Natta polymerization method, and is characterized in that there are almost no branched chains on the molecular chain, so the molecular chain arrangement is regular, and it has high density, melting point and high crystallinity. Therefore, the HDPE has good heat resistance, cold resistance, good chemical stability, higher rigidity and toughness and good mechanical strength; the dielectric property and the electrical insulation property are good, and the environmental stress cracking resistance is also good.
The thermoplastic elastomer is an elastomer having rubber elasticity at normal temperature and being moldable at high temperature. Different from the traditional vulcanized rubber, the thermoplastic elastomer has the characteristics of convenience in processing common plastics, wide processing mode, cyclic and repeated utilization and the like. For example: the SBS is a variety with the largest yield, the lowest cost and wider application, and is a styrene-butadiene-styrene triblock copolymer obtained by polymerizing styrene and butadiene as monomers. In the thermoplastic styrene-butadiene elastomer SBS, a hard segment is a Polystyrene (PS) chain segment, and a soft segment is a Polybutadiene (PB) chain segment. Due to the nature of block copolymerization, SBS possesses two glass transition temperatures (Tg), around 100 ℃ and-90 ℃ respectively. At normal temperature, the PS chain segment is in a glass state and plays a role of physical crosslinking, thereby providing excellent rigidity and strength for SBS; and the PB chain segment is in a high-elasticity state and is used as a soft segment to provide elasticity for SBS. When the temperature exceeds the Tg of the PS segment, the physical crosslinking is disentangled, the crosslinked network disappears, and the SBS has fluidity again. This is also the reason why SBS has rubber elasticity and plastic strength at normal temperature and can be plasticized and flow molded again at high temperature. SBS has excellent tensile strength, very large elongation at break, good elasticity, small permanent deformation, good flexibility and rebound resilience, large surface friction coefficient, excellent electrical insulation performance and the like.
The original particle size, content (volume fraction or mass fraction) and dispersion state of the conductive filler (conductive carbon black) in the composite conductive polymer material determine the conductivity of the composite material. It is known from classical percolation theory that when isolated dispersed filler particles are loosely packed in a material, a continuous conductive network may be formed when the volume dispersion of the conductive filler reaches a certain critical content. For example, after a certain volume fraction or mass fraction of conductive carbon black is added into polyolefin resin (such as polyethylene, polypropylene and the like), the matrix resin has conductivity, and the addition of a large amount of conductive filler can greatly reduce the impact property of the resin, remarkably increase the brittleness, limit the application range and reduce the fluidity of the composite material; the thermoplastic elastomer is added with a certain volume fraction or mass fraction of conductive carbon black to have conductive performance, and simultaneously, the elasticity and the flowability of the thermoplastic elastomer are obviously reduced due to the addition of a large amount of conductive filler, so that the processing and further application of the thermoplastic elastomer are influenced. In addition, the use of large amounts of conductive fillers also increases the cost of the conductive polymer composite.
In a non-fully compatible two polymer blend architecture, the lesser amount of component tends to be present in the continuous phase matrix as a dispersed phase, as islands are scattered in the ocean, hence the name "sea-island" structure. By utilizing the formation of a 'sea-island' structure, the polymer matrix can be modified, so that the performance of the polymer matrix is more excellent. Wherein, the toughener toughens and modifies the polymer matrix as the most typical example, such as a small amount of SBS, ethylene propylene rubber toughened polypropylene and the like; there are also resin reinforced rubbers such as a small amount of polyvinyl chloride resin reinforced nitrile rubber, a small amount of PS resin reinforced SBS thermoplastic elastomer, and the like. Thermoplastic elastomers are generally obtained by increasing the molecular weight during polymerization in order to improve and maintain strength at room temperature, high elastic deformation and other properties, but the increase in molecular weight tends to deteriorate the processing flowability of the thermoplastic elastomer. For example, in order to improve the processability of SBS, naphthenic oil or a low molecular weight polystyrene resin (PS) is added to its formulation. Compared with the addition of naphthenic oil, the addition of the low molecular weight PS resin is beneficial to improving the fluidity of SBS, and simultaneously, the mechanical properties such as tensile strength and the like are not greatly reduced. The PS resin is added into the thermoplastic elastomer SBS, namely the respective characteristics of the resin and the rubber (the thermoplastic elastomer) are utilized, and the purpose of mutually making up for the deficiencies is achieved by a blending method. When SBS is used as toughening modifier of PP, 20 wt% of SBS exists in form of disperse phase, which can greatly improve normal temperature impact property of PP continuous phase matrix. When the polyolefin resin and the thermoplastic elastomer mutually make up for the weakness by a blending method, if a small amount of conductive material is directly added, the conductivity of the polyolefin resin and the thermoplastic elastomer is far from the use requirement; if a large amount of conductive materials are added, the excellent performance of the composite material is greatly reduced, and the cost is greatly increased.
Therefore, aiming at the problems that the conductive filler is less in use amount and the conductive performance cannot meet the use requirement in the process of the conductive polymer composite material; although the conductive performance can meet the use requirement due to large conductive usage amount, when the mechanical property of the material is poor and the cost is increased, a new processing method needs to be developed to prepare the conductive thermoplastic elastomer, so that the usage amount of the conductive filler can be reduced, and the conductive performance of the material can be improved.
Disclosure of Invention
The invention aims to solve the problems and the defects in the prior art, and provides a method for preparing a conductive thermoplastic elastomer by combining a prefabricated master batch with phase structure regulation and control, wherein the method can be used in occasions with characteristics by reducing the using amount of a conductive filler and obviously improving the conductivity of a polymer composite material, so that the application range of the conductive thermoplastic elastomer can be enlarged; meanwhile, the preparation method is simple and easy to implement, can be used for producing the modified plastic by utilizing the common equipment (comprising an open type plastic refining machine, a closed type mixing mill, a double-screw extruder and the like) and process of the existing modified plastic, and is convenient to operate.
The invention is realized by the following technical scheme:
the invention discloses a method for preparing a conductive thermoplastic elastomer by combining prefabricated master batch and phase structure regulation, which comprises the following steps of:
firstly, evenly mixing polyolefin resin, a conductive material and an auxiliary agent to prepare a mixture;
secondly, uniformly blending the mixture to prepare a master batch;
thirdly, uniformly blending the master batch and the thermoplastic elastomer to prepare the conductive thermoplastic elastomer;
or
Firstly, uniformly mixing a thermoplastic elastomer, a conductive material and an auxiliary agent to prepare a mixture;
secondly, uniformly blending the mixture to prepare a master batch;
and thirdly, uniformly blending the master batch and the polyolefin resin to obtain the conductive thermoplastic elastomer.
The above method of the invention, further technical scheme is that the thermoplastic elastomer and the polyolefin resin are not completely compatible and when the difference between the volume ratio or the volume ratio of the thermoplastic elastomer and the polyolefin resin is less than or equal to 10%, the blend presents a bicontinuous phase structure, the polyolefin resin has a lower molecular weight than the thermoplastic elastomer, the polyolefin resin has a higher fluidity than the thermoplastic elastomer, the polyolefin resin and the thermoplastic elastomer have a fluidity difference, the polyolefin resin with high fluidity partially continuously migrates to the outer surface in the blending molding process, while the thermoplastic elastomer with low fluidity and the polyolefin resin with the rest part remain in the interior or in the middle, and finally the sandwich structure composite material A-B-A with a special structure is formed.
In the above method of the present invention, a further technical scheme may be that the polyolefin resin is one or a combination of homo-polypropylene and high density polyethylene; the thermoplastic elastomer is a styrene-butadiene thermoplastic elastomer, namely a styrene-butadiene-styrene triblock copolymer, and the mass ratio of styrene/butadiene in the structure is 20/80-40/60. The method is characterized in that the homopolymerized polypropylene is high-fluidity homopolymerized polypropylene with the number average molecular weight Mn of 50000-; the high-density polyethylene is high-flow polyethylene with the number-average molecular weight Mn of 50000-; the thermoplastic elastomer is a low-fluidity non-oil-extended polymer with the number-average molecular weight Mn of 260000-300000, the weight-average molecular weight Mw of 270000-310000 and the width of molecular weight distribution, i.e. d-Mw/Mn of less than or equal to 1.1. The above method of the present invention, further technical solution thereof, may further include the steps of:
firstly, mixing polyolefin resin, a conductive material and an auxiliary agent in a high-speed mixer at a low speed and a temperature of 20-50 ℃ for 3-5 min, and uniformly mixing to obtain a mixture;
secondly, adding the mixture into an open type plastic mixing machine or a closed type plastic mixing machine or a double-screw extruder at the temperature of 160-200 ℃, and uniformly blending the mixture through the shearing force of equipment to obtain master batch;
thirdly, adding the master batch and the thermoplastic elastomer into an open type plastic mixing mill or a closed type plastic mixing mill or a double-screw extruder at the temperature of 160-200 ℃ and uniformly blending through shearing action to obtain the conductive thermoplastic elastomer;
or
Firstly, mixing a thermoplastic elastomer, a conductive material and an auxiliary agent in a high-speed mixer at a low speed and a temperature of 20-50 ℃ for 3-5 min, and uniformly mixing to obtain a mixture;
secondly, adding the mixture into an open type plastic mixing machine or a closed type plastic mixing machine or a double-screw extruder at the temperature of 160-200 ℃, and uniformly blending the mixture through the shearing force of equipment to obtain master batch;
and thirdly, adding the master batch and the polyolefin resin into an open type plastic refining machine or a closed type plastic refining machine or a double-screw extruder at the temperature of 160-200 ℃ and uniformly blending through shearing action to obtain the conductive thermoplastic elastomer.
The method of the invention can be further characterized in that the conductive material is conductive carbon black; the auxiliary agent comprises an antioxidant and zinc stearate. The further technical proposal is that the conductive carbon black has the particle diameter of 20-25nm and the specific surface area of 600-800m2(iv) an oil absorption per gram of carbon black of 360-400 g, calculated as dibutyl phthalate.
The conductive thermoplastic elastomer prepared by the method is prepared from the following raw materials in parts by mass:
compared with the prior art, the invention has the following beneficial effects:
although for multi-component heterogeneous polymer blends, the less-abundant component tends to form the dispersed phase and the more abundant component tends to form the continuous phase, there are more factors that affect the phase structure and morphology. The method is characterized in that the structural model of the heterogeneous multicomponent polymer in an organizational mode provides that: the content of the dispersion phase is below 26% (volume fraction), the content of the continuous phase is above 74%, and the content of the continuous phase is 26-74% according to the conditions of intermolecular force, viscosity, temperature and the like. If the two are close to the same composition ratio, an interpenetrating network-like bicontinuous phase structure tends to be formed.
The sandwich structure composite material is a typical layered structure and can be divided into the following parts according to the material performance and characteristics: A-B-C or A-B-A, where the skin and core layers are usually different homogeneous materials, may also be considered as a special bicontinuous phase structure. For example, in SBS/PP blend systems, the incomplete compatibility of SBS and PP is exploited to give the blend a bicontinuous phase structure when the two are close to equal volume ratios. Furthermore, the fluidity difference caused by controlling the molecular weight of the PP and the SBS is utilized, part of the PP with high fluidity continuously migrates to the outer surface in the forming process, and the SBS with low fluidity and the rest of the PP are retained in the middle to form the sandwich structure composite material A-B-A with a special structure. The concrete structure is expressed as follows: layer (upper layer): PP continuous phase, SBS dispersed phase; layer B (intermediate layer): PP continuous phase, SBS continuous phase; layer a (lower layer): the detailed structure diagram of the PP continuous phase and the SBS dispersed phase is shown in figure 1 (a). FIG. 1(b) is formed if the conductive carbon black can be selectively dispersed in the PP matrix; on the contrary, if the conductive carbon black can be selectively dispersed in the SBS matrix, fig. 1(c) is formed. If the phase structure regulation method is adopted to prepare the conductive thermoplastic elastomer shown in the figures 1(b) and (c), because only one phase is needed to bear the necessary conductive network, the consumption of the conductive carbon black is greatly reduced; meanwhile, due to the fact that the viscosity difference between the PP and the SBS is controlled to enable the PP to be enriched to the surface, the conductive carbon black is selected to be capable of being selectively dispersed in the PP matrix in the method of (b) in the figure 1, and the conductive performance of the thermoplastic elastomer is better.
On the basis of the mechanism for preparing the conductive thermoplastic elastomer by the phase structure regulation and control method, the invention implements four processing methods for comparison: firstly, uniformly dispersing PP resin, carbon black, an antioxidant and a lubricant by virtue of an open type plastic mixer, a closed type mixer or a double-screw extruder, and then uniformly blending the PP resin and SBS, as shown in figure 2 (a); secondly, the SBS resin, the carbon black, the antioxidant and the lubricant are uniformly dispersed by an open type plastic mixer or a closed type mixer or a double-screw extruder, and then are uniformly blended with the PP, as shown in figure 2 (b); dispersing PP resin, SBS, antioxidant and lubricant uniformly by means of open type plastic mixer or closed type mixer or double screw extruder, then blending with carbon black uniformly, as shown in figure 2 (c); and fourthly, adding the PP resin and the SBS together with the carbon black, the antioxidant and the lubricant, and uniformly dispersing by virtue of an open type plastic mixer or a closed type mixer or a double-screw extruder, as shown in the figure 2 (d). Through analysis, the following results are obtained: if 10 parts of conductive carbon black is added to 100 parts of PP or 100 parts of SBS or 100 parts of PP/SBS (50/50) and uniformly dispersed in the polymer matrix, the concentration of the conductive carbon black is 9.1 wt%; if 10 parts of conductive carbon black is adopted to be firstly dispersed in 50 parts of PP (or 50 parts of SBS) and then blended with 50 parts of SBS (or 50 parts of PP), although the concentration of the conductive carbon black is still 9.1 wt%, the concentration of the conductive carbon black in the PP phase (or SBS phase) reaches 16.7% after the PP and SBS form a bicontinuous phase, and the conductivity of the composite material is obviously improved, as shown in figures 2(a) and 2 (b).
If the pre-masterbatch approach is not used, as in the preparation process and the addition sequence of FIGS. 2(c) and 2(d), the conductive carbon black concentration is 9.1 wt%; after 28 days of extraction with toluene, the SBS was completely extracted, which is different from the case where SBS was first mixed with carbon black. If SBS mixes with carbon black first, carbon black will form some carbon black gel with SBS, SBS can not be extracted by good solvent toluene totally; from the analysis of the results of the extraction experiments, it can be seen that the carbon black in fig. 2(c) and 2(d) is also dispersed in the PP matrix due to the viscosity difference, in other words, even though the concentration of the conductive carbon black in the PP phase is also 16.7%, the conductivity of the composite material is not significantly improved, and is very different from the conductivity of the thermoplastic elastomer prepared in fig. 2(a) and 2 (b). Aiming at the difference existing in the preparation of the conductive thermoplastic elastomer by combining the prefabricated master batch with the phase structure regulation and control in the figure 2, the dispersibility (also called as dispersion grade) of the carbon black is measured by adding a PP dilution method by adopting the method specified in the international standard ISO 18553-2002, the content of the carbon black is controlled to be 2.0 wt%, the dispersibility of the carbon black specified by the standard is divided into 0-7 grades, wherein the 0-grade dispersibility is the best, and the 7-grade dispersibility is the worst. The microphotographs of the carbon black dispersion samples prepared by the processes of fig. 2(a), 2(b), and 2(c) are shown in fig. 3(a), 2(b), and 2(c), and although the carbon black content is the same and is dispersed in the PP phase, the thermoplastic elastomers prepared by the processes of fig. 2(a) and 2(b) have conductivity. This is because the thermoplastic elastomer carbon black prepared by the processes of fig. 2(a) and 2(b) has good dispersibility, respectively, 4-grade and 5-grade, and the carbon black particles form a continuous and perfect conductive network, so the thermoplastic elastomer has good conductivity; the dispersibility of the carbon black for preparing the thermoplastic elastomer by the 2(c) process is not good and reaches 7 grades, and the thermoplastic elastomer does not have conductivity because the carbon black particles cannot form a continuous and perfect conductive network. The reason why the carbon black prepared by the 2(c) process has poor dispersibility is that although the large difference between the number average molecular weights of PP and SBS can control the dispersion of the conductive carbon black in the PP phase, the elastic rheological effect caused by SBS at high temperature further hinders the influence of the shearing force on the dispersion of the carbon black in the PP matrix.
In conclusion, the prefabricated master batch and the phase structure regulation and control are combined to prepare the conductive thermoplastic elastomer, so that the consumption of conductive carbon black can be reduced, the electrothermal plastic elastomer is improved, and the conductive thermoplastic elastomer is greatly superior to products available in the market at present. Meanwhile, the formula cost for preparing the conductive thermoplastic elastomer by combining the prefabricated master batch and phase structure regulation and control is relatively low, and the preparation process is simple.
Drawings
FIG. 1 is a schematic diagram of the principle of preparing conductive thermoplastic elastomer by phase structure regulation method
FIG. 2 is a schematic diagram of the preparation of conductive thermoplastic elastomer by the combination of the prefabricated master batch and the phase structure regulation
FIG. 3 is a photomicrograph showing the dispersibility of carbon black, in which (a) is example 1, (b) is example 2, and (c) is comparative example 6
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.
Example 1
The raw material formula (mass ratio, parts): 50 parts of HDPE resin (Mn 50000, Mw 330000, d 6.6, and Xc 73.3%), 50 parts of thermoplastic elastomer SBS (Mn 300000, Mw 310000, and d 1.01), and carbon black (particle size 20nm, specific surface area 800 m)2The oil absorption value is 400g/g)10, an antioxidant 3000.5 and zinc stearate 2.0.
The preparation process comprises the following steps: firstly, adding HDPE, carbon black, antioxidant and zinc stearate into a high-speed mixer, mixing for 3min at 50 ℃ and low speed, and discharging the uniformly mixed materials into a storage bin; secondly, adding the HDPE-carbon black mixture into an open type plastic mixing mill or a closed type plastic mixing mill or a double-screw extruder at the temperature of 160-180 ℃, and uniformly blending the HDPE-carbon black mixture through the shearing force of equipment to obtain HDPE/carbon black master batch; and thirdly, adding the HDPE/carbon black master batch and SBS resin into another open type plastic refining machine or closed type plastic refining machine or double-screw extruder at the temperature of 160-180 ℃ and uniformly blending through shearing action to obtain the conductive thermoplastic elastomer. The properties of the test sample are shown in Table 1.
Example 2
The raw material formula (mass ratio, parts): 50 parts of PP resin (Mn 60000, Mw 380000, d 6.3, Xc 52.5%), 50 parts of thermoplastic elastomer SBS (S/B40/60, Mn 260000, Mw 270000, d 1.04), and 50 parts of carbon black (particle size 25nm, specific surface area 600 m)2The oil absorption value of 360g/g) of 10, an antioxidant 3000.5 and zinc stearate 1.0.
The preparation process comprises the following steps: firstly, adding SBS, carbon black, antioxidant and zinc stearate into a high-speed mixer, mixing for 5min at 20 ℃ and low speed, and discharging the uniformly mixed materials into a bin; secondly, adding the SBS-carbon black mixture into an open type plastic mixing mill or a closed type plastic mixing mill or a double-screw extruder at the temperature of 180-200 ℃, and uniformly blending the mixture through the shearing force of equipment to obtain SBS/carbon black master batch; and thirdly, adding the SBS/carbon black master batch and the PP resin into another open type plastic refining machine or closed type plastic refining machine or double-screw extruder at the temperature of 180-200 ℃ and uniformly blending through shearing action to obtain the conductive thermoplastic elastomer. The properties of the test sample are shown in Table 1.
Example 3
The raw material formula (mass ratio, parts): PP resin (Mn 55000, Mw 350000, d 6.4, Xc 53.9%) 30, HDPE resin (Mn 53000, Mw 325000, d 6.1, Xc 71.9%) 10, thermoplastic elastomer SBS (S/B30/70, Mn 275000, Mw 293000, d 1.07)60, carbon black (particle size 22nm, specific surface area 700 m) 602385g/g of oil absorption value) 12, an antioxidant 3000.5 and zinc stearate 1.5.
The preparation process comprises the following steps: firstly, adding SBS, carbon black, antioxidant and zinc stearate into a high-speed mixer, mixing for 4min at 30 ℃ and low speed, and discharging the uniformly mixed materials into a storage bin; secondly, adding the SBS-carbon black mixture into an open type plastic mixing mill or a closed type plastic mixing mill or a double-screw extruder at the temperature of 180-200 ℃, and uniformly blending the mixture through the shearing force of equipment to obtain SBS/carbon black master batch; and thirdly, adding SBS/carbon black master batch, PP and HDPE resin into another open type plastic refining machine or closed type plastic refining machine or double screw extruder at the temperature of 180-200 ℃ and uniformly blending through shearing action to obtain the conductive thermoplastic elastomer. The performance of the product is shown in Table 1
Example 4
The raw material formula (mass ratio, parts): PP resin (Mn: 58500, Mw: 275400, d: 6.4, Xc: 52.8%) 45, thermoplastic elastomer SBS (S/B: 20/80, Mn: 285000, Mw: 308000, d: 1.08)55, carbon black (particle size 25nm, specific surface area 750 m) 552The oil absorption value is 390g/g)11, an antioxidant 3000.5 and zinc stearate 1.5.
The preparation process comprises the following steps: firstly, adding SBS, carbon black, antioxidant and zinc stearate into a high-speed mixer, mixing for 3min at 40 ℃ and low speed, and discharging the uniformly mixed materials into a storage bin; secondly, adding the SBS-carbon black mixture into an open type plastic mixing mill or a closed type plastic mixing mill or a double-screw extruder at the temperature of 180-200 ℃, and uniformly blending the mixture through the shearing force of equipment to obtain SBS/carbon black master batch; and thirdly, adding the SBS/carbon black master batch and the PP resin into another open type plastic refining machine or closed type plastic refining machine or double-screw extruder at the temperature of 180-200 ℃ and uniformly blending through shearing action to obtain the conductive thermoplastic elastomer. The properties of the test sample are shown in Table 1.
Example 5
The raw material formula (mass ratio, parts): 50% of HDPE resin (Mn 55000, Mw 335000, d 6.1, and Xc 74.0%), 5% of PP resin (Mn 52300, Mw 348000, d 6.65, and Xc 52.1%), 45% of thermoplastic elastomer SBS (S/B25/75, Mn 279000, Mw 300200, and d 1.08), and 45% of carbon black (particle size 20nm, specific surface area 600 m)2The oil absorption value of 370g/g) of 10, an antioxidant 3000.5 and zinc stearate 1.0.
The preparation process comprises the following steps: firstly, adding PP and HDPE, carbon black, antioxidant and zinc stearate into a high-speed mixer, mixing for 5min at 35 ℃ and low speed, and discharging the uniformly mixed materials into a storage bin; secondly, adding the polyolefin (PP, HDPE) -carbon black mixture into an open type plastic mixing machine or a closed type plastic mixing machine or a double-screw extruder at the temperature of 180-200 ℃, and uniformly blending the mixture through the shearing force of equipment to obtain polyolefin (PP, HDPE)/carbon black master batch; and thirdly, adding polyolefin (PP, HDPE)/carbon black master batch and SBS resin into another open type plastic refining machine or closed type plastic refining machine or double screw extruder at the temperature of 180-200 ℃ and uniformly blending through shearing action to obtain the conductive thermoplastic elastomer. The properties of the test sample are shown in Table 1.
Example 6
The raw material formula (mass ratio, parts): 60 parts of PP resin (Mn 55000, Mw 354000, d 6.44, Xc 50.6%), 40 parts of thermoplastic elastomer SBS (S/B35/65, Mn 265000, Mw 281000, d 1.06), and carbon black (particle size 20nm, specific surface area 800 m)2395g/g of oil absorption value, 3000.5 of antioxidant and 1.0 of zinc stearate.
The preparation process comprises the following steps: firstly, adding PP, carbon black, an antioxidant and zinc stearate into a high-speed mixer, mixing for 4min at 45 ℃ and low speed, and discharging the uniformly mixed materials into a storage bin; secondly, adding the PP-carbon black mixture into an open type plastic mixing mill or a closed type plastic mixing mill or a double-screw extruder at the temperature of 180-200 ℃, and uniformly blending the mixture through the shearing force of equipment to obtain PP/carbon black master batch; and thirdly, adding the PP/carbon black master batch and SBS resin into another open type plastic refining machine or closed type plastic refining machine or double-screw extruder at the temperature of 180-200 ℃ and uniformly blending through shearing action to obtain the conductive thermoplastic elastomer. The properties of the test sample are shown in Table 1.
Comparative example 1
The raw material formula (mass ratio, parts): 100 parts of PP resin (Mn is 55500, Mw is 350100, d is 6.3 and Xc is 53.7%), 3000.5 parts of antioxidant and 1.0 part of zinc stearate.
The preparation process comprises the following steps: firstly, adding PP, an antioxidant and zinc stearate into a high-speed mixer, mixing for 5min at 20 ℃ and low speed, and discharging the uniformly mixed materials into a bin; secondly, adding the PP mixture into an open type plastic refining machine or a closed type plastic refining machine or a double-screw extruder at the temperature of 180-200 ℃, and uniformly blending the PP mixture through the shearing force of equipment to obtain the PP mixture. The properties of the test sample are shown in Table 1.
Comparative example 2
The raw material formula (mass ratio, parts): thermoplastic elastomer SBS (S/B40/60, Mn 261000, Mw 277300 and d 1.06), antioxidant 3000.5 and zinc stearate 1.0.
The preparation process comprises the following steps: firstly, adding SBS, antioxidant and zinc stearate into a high-speed mixer, mixing for 5min at 20 ℃ and low speed, and discharging the uniformly mixed materials into a bin; secondly, adding the SBS mixture into an open type plastic refining machine or a closed type plastic refining machine or a double-screw extruder at the temperature of 160-180 ℃, and uniformly blending the SBS mixture through the shearing force of equipment to obtain the SBS mixture. The properties of the test sample are shown in Table 1.
Comparative example 3
The raw material formula (mass ratio, parts): 50 parts of PP resin (Mn is 55500, Mw is 350100, d is 6.3 and Xc is 53.7%), 50 parts of thermoplastic elastomer SBS (S/B is 30/70, Mn is 261000, Mw is 277300 and d is 1.06), 3000.5 parts of antioxidant and 1.0 part of zinc stearate.
The preparation process comprises the following steps: firstly, adding PP, SBS, antioxidant and zinc stearate into a high-speed mixer, mixing for 4min at 30 ℃ and low speed, and discharging the uniformly mixed materials into a storage bin; secondly, adding the PP and SBS mixture into an open type plastic refining machine or a closed type plastic refining machine or a double-screw extruder at the temperature of 180-200 ℃, and uniformly blending through the shearing force of equipment to obtain the PP/SBS mixture. The properties of the test sample are shown in Table 1.
Comparative example 4
The raw material formula (mass ratio, parts): thermoplastic elastomer SBS (S/B-20/80, Mn-261000, Mw-277300, d-1.06) 100, carbon black (particle size 25nm, specific surface area 800 m)2The oil absorption value is 390g/g) is 10, the antioxidant 3000.5 and the zinc stearate is 1.0.
The preparation process comprises the following steps: firstly, adding SBS, carbon black, antioxidant and zinc stearate into a high-speed mixer, mixing for 5min at 20 ℃ and low speed, and discharging the uniformly mixed materials into a storage bin; secondly, adding the SBS-carbon black mixture into an open type plastic mixing mill or a closed type plastic mixing mill or a double-screw extruder at the temperature of 160-180 ℃, and uniformly blending the SBS-carbon black mixture through the shearing force of equipment to obtain the SBS/carbon black mixture. The properties of the test sample are shown in Table 1.
Comparative example 5
The raw material formula (mass ratio, parts): 50 parts of PP resin (Mn 55500, Mw 350100, d 6.3, Xc 53.7%), 50 parts of thermoplastic elastomer SBS (S/B35/65, Mn 261000, Mw 277300, d 1.06), and 50 parts of carbon black (particle size 25nm, specific surface area 800 m)2The oil absorption value is 390g/g) is 10, the antioxidant 3000.5 and the zinc stearate is 1.0.
The preparation process comprises the following steps: firstly, adding PP, SBS, carbon black, antioxidant and zinc stearate into a high-speed mixer, mixing for 5min at 20 ℃ and low speed, and discharging the uniformly mixed materials into a bin; secondly, adding the PP-SBS-carbon black mixture into an open type plastic mixing machine or a closed type plastic mixing machine or a double-screw extruder at the temperature of 180-200 ℃, and uniformly blending through the shearing force of equipment to obtain the PP/SBS/carbon black mixture. The properties of the test sample are shown in Table 1.
Comparative example 6
The raw material formula (mass ratio, parts): 50 parts of PP resin (Mn 55500, Mw 350100, d 6.3, Xc 53.7%), 50 parts of thermoplastic elastomer SBS (S/B30/70, Mn 261000, Mw 277300, d 1.06), and 50 parts of carbon black (particle size 25nm, specific surface area 800 m)2The oil absorption value is 390g/g) is 10, the antioxidant 3000.5 and the zinc stearate is 1.0.
The preparation process comprises the following steps: firstly, adding PP, SBS, antioxidant and zinc stearate into a high-speed mixer, mixing for 4min at 20 ℃ and low speed, and discharging the uniformly mixed materials into a bin; secondly, adding the PP-SBS mixture into an open type plastic refining machine or a closed type plastic refining machine or a double-screw extruder at the temperature of 180-2000 ℃, and uniformly blending the mixture through the shearing force of equipment to obtain a PP/SBS mixture; thirdly, adding the PP/SBS blend and the carbon black into a high-speed mixer at the temperature of 20 ℃ and at a low speed and continuously mixing for 4 min; and fourthly, adding the PP/SBS-carbon black mixture into another open type plastic refining machine or closed type plastic refining machine or double-screw extruder at the temperature of 180-200 ℃, and uniformly blending through shearing action to obtain the PP/SBS/carbon black mixture. The properties of the test sample are shown in Table 1.
Table 1 summary of properties of conductive thermoplastic elastomers
Experimental conditions of solvent extraction: percentage mass loss of SBS after extraction in toluene solvent at 23 ℃ for 28 days and complete drying, where the values outside the parenthesis are the actual extraction yield in the experiment and the values in the parenthesis are the theoretical calculated extraction yield.
Table number of carbon black content: the outside-parenthesis value is the mass percentage content of carbon black calculated according to the formula theory, the inside-parenthesis value is the mass percentage content calculated according to the formula theory by combining the prefabricated master batch and the phase structure regulation and control to disperse the carbon black in the polyolefin (PE, PP) phase or the SBS phase and calculating according to the formula theory, wherein-P and-S respectively represent that the carbon black is completely dispersed in the polyolefin (PE, PP) phase and the SBS phase.
Claims (4)
1. A method for preparing a conductive thermoplastic elastomer by combining a prefabricated master batch and phase structure regulation and control is characterized by comprising the following steps of:
firstly, evenly mixing polyolefin resin, a conductive material and an auxiliary agent to prepare a mixture;
secondly, uniformly blending the mixture to prepare a master batch;
thirdly, uniformly blending the master batch and the thermoplastic elastomer to prepare the conductive thermoplastic elastomer;
or
Firstly, uniformly mixing a thermoplastic elastomer, a conductive material and an auxiliary agent to prepare a mixture;
secondly, uniformly blending the mixture to prepare a master batch;
thirdly, uniformly blending the master batch and the polyolefin resin to prepare the conductive thermoplastic elastomer;
wherein the thermoplastic elastomer and the polyolefin resin are not completely compatible, and when the volume ratio or the volume ratio difference between the thermoplastic elastomer and the polyolefin resin is less than or equal to 10%, the blend presents a bicontinuous phase structure, the polyolefin resin has a lower molecular weight than the thermoplastic elastomer, the polyolefin resin has a higher fluidity than the thermoplastic elastomer, the polyolefin resin and the thermoplastic elastomer have a fluidity difference, and the high fluidity of the polyolefin resin is utilized to ensure that the blend presents a bicontinuous phase structure in the middle of the blending molding processThe components continuously migrate to the outer surface, while the low-fluidity thermoplastic elastomer and the rest part of the polyolefin resin are remained in the interior or in the middle, and finally the sandwich core structure composite material A-B-A with a special structure is formed; the polyolefin resin is one or the combination of homopolymerized polypropylene and high-density polyethylene; the thermoplastic elastomer is a styrene-butadiene thermoplastic elastomer, namely a styrene-butadiene-styrene triblock copolymer, and the mass ratio of styrene/butadiene in the structure is 20/80-40/60; the homopolymerized polypropylene is high-fluidity homopolymerized polypropylene with the number average molecular weight Mn of 50000-60000, the weight average molecular weight Mw of 330000-380000 and the molecular weight distribution width d of Mw/Mn of more than or equal to 6.0, and the crystallinity Xc of differential scanning calorimetry, namely DSC test is more than or equal to 50 percent; the high-density polyethylene is high-flow polyethylene with the number-average molecular weight Mn of 50000-; the thermoplastic elastomer is a low-fluidity non-oil-extended polymer with the number-average molecular weight Mn of 260000-300000, the weight-average molecular weight Mw of 270000-310000 and the width of molecular weight distribution, namely d-Mw/Mn of less than or equal to 1.1; the conductive material is conductive carbon black, and the conductive carbon black has the particle size of 20-25nm and the specific surface area of 600-800m2(iv) an oil absorption per gram of carbon black of 360-400 g, calculated as dibutyl phthalate.
2. The method according to claim 1, characterized by comprising the steps of:
firstly, mixing polyolefin resin, a conductive material and an auxiliary agent in a high-speed mixer at a low speed and a temperature of 20-50 ℃ for 3-5 min, and uniformly mixing to obtain a mixture;
secondly, adding the mixture into an open type plastic mixing machine or a closed type plastic mixing machine or a double-screw extruder at the temperature of 160-200 ℃, and uniformly blending the mixture through the shearing force of equipment to obtain master batch;
thirdly, adding the master batch and the thermoplastic elastomer into an open type plastic mixing mill or a closed type plastic mixing mill or a double-screw extruder at the temperature of 160-200 ℃ and uniformly blending through shearing action to obtain the conductive thermoplastic elastomer;
or
Firstly, mixing a thermoplastic elastomer, a conductive material and an auxiliary agent in a high-speed mixer at a low speed and a temperature of 20-50 ℃ for 3-5 min, and uniformly mixing to obtain a mixture;
secondly, adding the mixture into an open type plastic mixing machine or a closed type plastic mixing machine or a double-screw extruder at the temperature of 160-200 ℃, and uniformly blending the mixture through the shearing force of equipment to obtain master batch;
and thirdly, adding the master batch and the polyolefin resin into an open type plastic refining machine or a closed type plastic refining machine or a double-screw extruder at the temperature of 160-200 ℃ and uniformly blending through shearing action to obtain the conductive thermoplastic elastomer.
3. The method of claim 1, wherein the adjuvant comprises an antioxidant and zinc stearate.
4. A conductive thermoplastic elastomer prepared by the method of any one of claims 1 to 3, characterized by being prepared from the following raw materials in parts by mass:
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| CN111234347A (en) | 2020-06-05 |
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