CN114133736B - Master batch for engineering plastics and preparation method thereof - Google Patents
Master batch for engineering plastics and preparation method thereof Download PDFInfo
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Abstract
The invention provides a master batch for engineering plastics and a preparation method thereof, wherein the raw materials comprise a resin matrix which takes amino modified polyphenylene sulfide (PPS-NH2) as a main part, a resin matrix which takes polybutylene terephthalate (PBT) as a secondary part, a carbon conductive filler, a carboxylated metal organic framework material (MOF-COOH), and corresponding auxiliary agents such as a dispersant, an antioxidant and the like; meanwhile, the preparation method is optimized, so that the dispersibility of the carbon conductive filler in the resin matrix is further improved, and the master batch for the engineering plastics, which has good conductivity and good re-dilution performance in the preparation of the conductive plastics, is prepared, so that the resistivity test value of the product is stabilized in an allowable range.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a master batch for engineering plastics and a preparation method thereof.
Background
The conductive plastic is a functional polymer material which is processed by a plastic processing method by mixing a resin and a conductive filler. The conductive filling materials mainly comprise three types of carbon materials, metals, antistatic agents and the like, however, the antistatic agents have the disadvantages of higher price, low melting point, poor thermal stability, difficult mixing with resin and poor universality; although the metallic filler has high conductivity, it has poor compatibility with the resin matrix and is easily oxidized to cause a decrease in conductivity; therefore, carbon-based materials are most commonly used because they are easily available in raw materials, light in weight, not easily oxidized, and easily form a conductive network, and commonly used carbon-based conductive fillers include conductive carbon black, carbon nanotubes, carbon fibers, graphene, graphite, and the like.
Polyphenylene Sulfide (PPS) is a novel high-performance thermoplastic resin, and has the advantages of high mechanical strength, high temperature resistance, chemical resistance, flame retardancy, good thermal stability, excellent electrical property and the like. When the conductive composite material is prepared in a traditional melt extrusion blending mode, a large amount of carbon conductive filler is simply filled into a polyphenylene sulfide resin matrix, so that the conductive filler is easy to agglomerate and is incompletely dispersed, and the conductive performance and the mechanical performance of the composite material are inevitably greatly reduced. Meanwhile, the carbon-based conductive filler has dust problem in the blending process with the polyphenylene sulfide resin, and is easy to cause environmental pollution.
On the other hand, in the prior art, because the conductive performance of the conductive plastic master batch is poor, excessive conductive plastic master batch is often added when the conductive plastic is prepared, so that the manufacturing cost is low, the performance of the product is unstable, and particularly, the resistivity test value of the product often has a large floating range.
Therefore, the prepared novel master batch for the engineering plastics has good conductivity and good re-dilution performance when the conductive plastics are prepared, so that the resistivity test value of the product is stable in an allowable range, and the preparation method has great application value.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a master batch for engineering plastics and a preparation method thereof, wherein the raw materials comprise a resin matrix taking amino modified polyphenylene sulfide (PPS-NH2) as a main component, a resin matrix taking polybutylene terephthalate (PBT) as a secondary component, a carbon conductive filler, a carboxylated metal organic framework material (MOF-COOH), a corresponding dispersing agent, an antioxidant and other auxiliary agents; meanwhile, the preparation method is optimized, so that the dispersibility of the carbon-series conductive filler in the resin matrix is further improved, and the master batch for the engineering plastics, which has good conductivity and good re-dilution performance in the preparation of the conductive plastics, is prepared, so that the resistivity test value of the product is stabilized in an allowable range.
In order to achieve the purpose, the invention adopts the following technical scheme that the master batch for the engineering plastics comprises the following raw materials in parts by weight:
80-100 parts of amino modified polyphenylene sulfide, 30-50 parts of polybutylene terephthalate, 80-100 parts of graphite powder, 10-20 parts of carbon nano tube, 10-15 parts of dispersing agent, 3-6 parts of carboxylated metal organic framework material, 3-6 parts of silane coupling agent, 0.2-0.5 part of antioxidant and 0.1-0.5 part of ester exchange inhibitor;
the dispersing agent is amino modified polyester resin, and the weight average molecular weight is 6000g/mol 5000-6000 g/mol; the preparation method of the dispersant comprises the following steps:
(1) weighing the following raw materials in parts by weight: 5-10 parts of polyether glycol, 15-25 parts of adipic acid, 30-50 parts of terephthalic acid, 10-20 parts of butanediol, 12-18 parts of hexanediol, 3-5 parts of neopentyl glycol, 3-5 parts of dimethylolpropionic acid, 20-30 parts of diphenylmethane diisocyanate, 30-50 parts of tetraethylenepentamine, 0.02-0.05 part of tetrabutyl titanate and 80-100 parts of dimethylbenzene;
(2) sequentially adding polyether dihydric alcohol, adipic acid, terephthalic acid, butanediol, hexanediol, neopentyl glycol, tetrabutyl titanate and half of xylene into a reaction container, introducing nitrogen, heating to 180 +/-10 ℃, carrying out heat preservation reaction for 12-15h, and continuously removing moisture through a water separator in the reaction process; adding dimethylolpropionic acid, continuously heating to 200 +/-10 ℃, reacting for 6-8h, and after the reaction is finished, carrying out reduced pressure distillation to remove xylene and unreacted micromolecules to obtain polyether modified polyester;
(3) mixing the polyether modified polyester prepared in the step (2), diphenylmethane diisocyanate and the rest xylene, adding the mixture into a reaction vessel, introducing nitrogen, heating to 50 +/-2 ℃, and reacting for 2-4 h; finally, adding tetraethylenepentamine, heating to 70 +/-2 ℃, reacting for 2-3h, and distilling under reduced pressure to remove xylene and unreacted micromolecules to obtain the dispersing agent.
Preferably, the number average molecular weight of the polyether glycol is 200-300 g/mol.
The number average molecular weight of the amino modified polyphenylene sulfide is 15000-20000 g/mol; the number average molecular weight of the polybutylene terephthalate is 20000-30000g/mol,
the graphite powder is formed by mixing 100-300nm graphite powder A and 1-3 mu m graphite powder B according to the weight ratio of 5-7: 1; the diameter of the outer tube of the carbon nano tube is 10-50nm, and the length of the outer tube is 1-3 mu m;
preferably, the surface of the graphite powder or the carbon nano tube is subjected to oxidation treatment, so that a carboxyl functional group is grafted on the surface;
the silane coupling agent is at least one selected from gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane.
The antioxidant is at least one selected from phenolic antioxidants, phosphite antioxidants and sulfur-containing ester antioxidants; preferably, at least one selected from the group consisting of 2, 6-di-t-butylphenol, 2, 6-di-t-butyl-4-ethylphenol, 4-hydroxymethyl-2, 6-di-t-butylphenol, 2, 6-di-t-butyl-4-n-butylphenol, triphenyl phosphite, tris (nonylphenyl) phosphite, triisooctyl phosphite, triisodecyl phosphite, diisodecyl phosphite, dilauryl thiodipropionate, and distearyl thiodipropionate.
The ester exchange inhibitor is at least one selected from sodium dihydrogen phosphate, sodium hexametaphosphate and ammonium hypophosphite.
Preferably, the master batch for engineering plastics comprises the following raw materials in parts by weight:
100 parts of amino modified polyphenylene sulfide, 50 parts of polybutylene terephthalate, 80 parts of graphite powder, 15 parts of carbon nano tube, 13 parts of dispersing agent, 5 parts of carboxylated metal organic framework material, 6 parts of silane coupling agent, 0.5 part of antioxidant and 0.3 part of ester exchange inhibitor.
The invention also aims to provide a preparation method of the master batch for the engineering plastics, which comprises the following steps:
(1) weighing 80-100 parts of amino modified polyphenylene sulfide, 30-50 parts of polybutylene terephthalate, 80-100 parts of graphite powder, 10-20 parts of carbon nano tube, 10-15 parts of dispersing agent, 3-6 parts of carboxylated metal organic framework material, 3-6 parts of silane coupling agent, 0.2-0.5 part of antioxidant and 0.1-0.5 part of ester exchange inhibitor according to parts by weight;
(2) uniformly mixing graphite powder, carbon nanotubes and a silane coupling agent, performing ball milling at 0-5 ℃ for 10-20min, adding xylene which is 3-5 times of the total weight of the graphite powder and the carbon nanotubes, a carboxylated metal organic framework material and a dispersing agent, and performing ultrasonic dispersion for 20-40 min; then adding amino modified polyphenylene sulfide, polybutylene terephthalate, an antioxidant and an ester exchange inhibitor, heating to 180 ℃ and 200 ℃, refluxing and stirring for 10-20min, continuously stirring to remove xylene, then transferring to an internal mixer for mixing for 40-60min, and controlling the mixing temperature at 290 ℃ and 300 ℃;
(3) and (3) transferring the banburying product obtained in the step (2) to a double-screw extruder for extrusion granulation to obtain master batches for engineering plastics.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a master batch for engineering plastics and a preparation method thereof, wherein the raw materials comprise a resin matrix which takes amino modified polyphenylene sulfide (PPS-NH2) as a main part, a resin matrix which takes polybutylene terephthalate (PBT) as a secondary part, a carbon conductive filler, a carboxylated metal organic framework material (MOF-COOH), and corresponding auxiliary agents such as a dispersant, an antioxidant and the like; meanwhile, the preparation method is optimized, so that the dispersibility of the carbon-series conductive filler in the resin matrix is further improved, and the master batch for the engineering plastics, which has good conductivity and good re-dilution performance in the preparation of the conductive plastics, is prepared, so that the resistivity test value of the product is stabilized in an allowable range.
(2) According to the invention, the toughness of the amino modified polyphenylene sulfide resin is improved by taking polybutylene terephthalate (PBT) as a secondary resin matrix, and a resin system compounded by the PBT and the amino modified polyphenylene sulfide resin has good compatibility with the carbon conductive filler, so that the carbon conductive filler can be well dispersed; meanwhile, the carboxylated metal organic framework material (MOF-COOH) is added, so that the interfacial compatibility of the PPS-NH2 and the PBT can be improved, and the original mechanical properties can be better maintained after the carbon conductive filler is added.
(3) According to the invention, graphite powder with different particle sizes and a reasonable proportion are selected, so that the close packing of conductive particles can be realized, the agglomeration of conductive fillers is prevented, and a good conductive network is formed; the invention adopts amino modified polyester as dispersant, the polyether chain segment is connected in the solvation chain of the polyester, and the amino is used as an anchoring group, so that the polyester can generate chemical reaction with carboxyl, silane and other groups on the surface of graphite powder or carbon nano tube, and the good dispersion of the conductive filler is realized.
(4) The method has the advantages that the xylene is added in the preparation process of the master batch to promote the dispersion of the graphite powder or the carbon nano tube, and the xylene is removed again before banburying and mixing, so that the dispersion effect of the graphite powder or the carbon nano tube is further improved, the process is simple, the cost is lower, the method is suitable for large-scale industrial production, and the method has good economic benefit and wide market prospect.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the present invention and is not intended to limit the scope of the claims which follow. All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
1. Preparation of the dispersant
1.1 Process for the preparation of dispersant I, comprising the steps of:
(1) weighing the following raw materials in parts by weight: 8 parts of polyether glycol, 20 parts of adipic acid, 40 parts of terephthalic acid, 14 parts of butanediol, 12 parts of hexanediol, 4 parts of neopentyl glycol, 4 parts of dimethylolpropionic acid, 25 parts of diphenylmethane diisocyanate, 40 parts of tetraethylenepentamine, 0.03 part of tetrabutyl titanate and 90 parts of xylene; the number average molecular weight of the polyether glycol is 210 g/mol;
(2) sequentially adding polyether glycol, adipic acid, terephthalic acid, butanediol, hexanediol, neopentyl glycol, tetrabutyl titanate and half xylene into a reaction container, introducing nitrogen, heating to 180 +/-10 ℃, carrying out heat preservation reaction for 14 hours, and continuously removing moisture through a water separator in the reaction process; adding dimethylolpropionic acid, continuously heating to 200 +/-10 ℃, reacting for 8 hours, and after the reaction is finished, carrying out reduced pressure distillation to remove xylene and unreacted micromolecules to obtain polyether modified polyester;
(3) mixing the polyether modified polyester prepared in the step (2), diphenylmethane diisocyanate and the rest xylene, adding the mixture into a reaction vessel, introducing nitrogen, heating to 50 +/-2 ℃, and reacting for 4 hours; finally, adding tetraethylenepentamine, heating to 70 +/-2 ℃, reacting for 3h, and distilling under reduced pressure to remove xylene and unreacted small molecules to obtain the dispersing agent I, wherein the weight average molecular weight of the dispersing agent I is 5634 g/mol.
1.2 Process for the preparation of dispersant II, comprising the steps of:
(1) weighing the following raw materials in parts by weight: 10 parts of polyether glycol, 20 parts of adipic acid, 45 parts of terephthalic acid, 15 parts of butanediol, 18 parts of hexanediol, 5 parts of neopentyl glycol, 3 parts of dimethylolpropionic acid, 30 parts of diphenylmethane diisocyanate, 30 parts of tetraethylenepentamine, 0.05 part of tetrabutyl titanate and 100 parts of dimethylbenzene; the number average molecular weight of the polyether glycol is 300 g/mol;
(2) sequentially adding polyether dihydric alcohol, adipic acid, terephthalic acid, butanediol, hexanediol, neopentyl glycol, tetrabutyl titanate and half xylene into a reaction container, introducing nitrogen, heating to 180 +/-10 ℃, carrying out heat preservation reaction for 15 hours, and continuously removing moisture through a water separator in the reaction process; adding dimethylolpropionic acid, continuously heating to 200 +/-10 ℃, reacting for 7 hours, and after the reaction is finished, removing dimethylbenzene and unreacted micromolecules by reduced pressure distillation to obtain polyether modified polyester;
(3) mixing the polyether modified polyester prepared in the step (2), diphenylmethane diisocyanate and the rest xylene, adding the mixture into a reaction vessel, introducing nitrogen, heating to 50 +/-2 ℃, and reacting for 3 hours; and finally adding tetraethylenepentamine, heating to 70 +/-2 ℃, reacting for 3h, and distilling under reduced pressure to remove xylene and unreacted micromolecules to obtain the dispersing agent II, wherein the weight average molecular weight of the dispersing agent II is 5829 g/mol.
Example 1
The master batch for the engineering plastics comprises the following raw materials in parts by weight: 100 parts of amino modified polyphenylene sulfide, 50 parts of polybutylene terephthalate, 80 parts of graphite powder, 15 parts of carbon nano tube, 13 parts of dispersing agent I, 5 parts of carboxylated metal organic framework material, 6 parts of silane coupling agent, 0.5 part of antioxidant and 0.3 part of ester exchange inhibitor;
the number average molecular weight of the amino modified polyphenylene sulfide is 18000 g/mol; the number average molecular weight of the polybutylene terephthalate is 23000 g/mol;
the graphite powder is formed by mixing graphite powder A with the particle size of 200nm and graphite powder B with the particle size of 1 mu m according to the weight ratio of 6: 1; the diameter of the outer tube of the carbon nano tube is 40nm, and the length of the outer tube is 3 mu m; oxidizing the surface of the graphite powder or the carbon nano tube to graft a carboxyl functional group on the surface; the silane coupling agent is selected from gamma-glycidoxypropyltrimethoxysilane; the antioxidant is selected from 2, 6-di-tert-butylphenol; the ester exchange inhibitor is selected from sodium dihydrogen phosphate.
The preparation method of the master batch for the engineering plastics comprises the following steps:
(1) weighing the following raw materials, by weight, 100 parts of amino modified polyphenylene sulfide, 50 parts of polybutylene terephthalate, 80 parts of graphite powder, 15 parts of carbon nano tube, 13 parts of dispersing agent, 5 parts of carboxylated metal organic framework material, 6 parts of silane coupling agent, 0.5 part of antioxidant and 0.3 part of ester exchange inhibitor;
(2) uniformly mixing graphite powder, carbon nano tubes and a silane coupling agent, performing ball milling at 0 ℃ for 20min, adding dimethylbenzene, a carboxylated metal organic framework material and a dispersing agent I which are 4 times of the total weight of the graphite powder and the carbon nano tubes, and performing ultrasonic dispersion for 40 min; then adding amino modified polyphenylene sulfide, polybutylene terephthalate, an antioxidant and an ester exchange inhibitor, heating to 200 ℃, refluxing and stirring for 20min, continuously stirring to remove xylene, and then transferring to an internal mixer for mixing for 50min, wherein the internal mixing temperature is controlled at 290 ℃;
(3) and (3) transferring the banburying product obtained in the step (2) to a double-screw extruder for extrusion granulation to obtain master batches for engineering plastics.
Example 2
The master batch for the engineering plastics comprises the following raw materials in parts by weight: 90 parts of amino modified polyphenylene sulfide, 40 parts of polybutylene terephthalate, 80 parts of graphite powder, 15 parts of carbon nano tube, 12 parts of dispersing agent II, 6 parts of carboxylated metal organic framework material, 3 parts of silane coupling agent, 0.5 part of antioxidant and 0.3 part of ester exchange inhibitor;
the number average molecular weight of the amino modified polyphenylene sulfide is 20000 g/mol; the polybutylene terephthalate has a number average molecular weight of 27000g/mol,
the graphite powder is formed by mixing 100nm graphite powder A and 2 μm graphite powder B according to a weight ratio of 7: 1; the diameter of the outer tube of the carbon nano tube is 20nm, and the length of the outer tube is 1 mu m; oxidizing the surface of the graphite powder or the carbon nano tube to graft a carboxyl functional group on the surface;
the silane coupling agent is selected from gamma-aminopropyl triethoxysilane; the antioxidant is selected from triisooctyl phosphite; the transesterification inhibitor is selected from ammonium hypophosphite.
The preparation method of the master batch for the engineering plastic comprises the following steps:
(1) weighing the following raw materials, by weight, 90 parts of amino modified polyphenylene sulfide, 40 parts of polybutylene terephthalate, 80 parts of graphite powder, 15 parts of carbon nano tube, 12 parts of dispersing agent II, 6 parts of carboxylated metal organic framework material, 3 parts of silane coupling agent, 0.5 part of antioxidant and 0.3 part of ester exchange inhibitor;
(2) uniformly mixing graphite powder, carbon nanotubes and a silane coupling agent, ball-milling for 15min at 5 ℃, adding dimethylbenzene, a carboxylated metal organic framework material and a dispersing agent II, wherein the dimethylbenzene is 5 times of the total weight of the graphite powder and the carbon nanotubes, and ultrasonically dispersing for 30 min; then adding amino modified polyphenylene sulfide, polybutylene terephthalate, an antioxidant and an ester exchange inhibitor, heating to 190 ℃, refluxing and stirring for 20min, continuously stirring to remove xylene, and then transferring to an internal mixer for mixing for 40min, wherein the internal mixing temperature is controlled at 300 ℃;
(3) and (3) transferring the banburying product obtained in the step (2) to a double-screw extruder for extrusion granulation to obtain master batches for engineering plastics.
Example 3
The master batch for the engineering plastics comprises the following raw materials in parts by weight: 90 parts of amino modified polyphenylene sulfide, 34 parts of polybutylene terephthalate, 90 parts of graphite powder, 10 parts of carbon nano tube, 13 parts of dispersing agent I, 4 parts of carboxylated metal organic framework material, 5 parts of silane coupling agent, 0.4 part of antioxidant and 0.4 part of ester exchange inhibitor;
the number average molecular weight of the amino modified polyphenylene sulfide is 19000 g/mol; the polybutylene terephthalate has the number average molecular weight of 30000g/mol, and the graphite powder is formed by mixing graphite powder A with the particle size of 180nm and graphite powder B with the particle size of 2 mu m according to the weight ratio of 7: 1; the diameter of the outer tube of the carbon nano tube is 30nm, and the length of the outer tube is 1 mu m; the silane coupling agent is selected from gamma-aminopropyltriethoxysilane; the antioxidant is selected from 2, 6-di-tert-butyl-4-ethylphenol; the ester exchange inhibitor is selected from sodium dihydrogen phosphate.
The preparation method of the master batch for the engineering plastics comprises the following steps:
(1) weighing the following raw materials, by weight, 90 parts of amino modified polyphenylene sulfide, 34 parts of polybutylene terephthalate, 90 parts of graphite powder, 10 parts of carbon nano tube, 13 parts of dispersing agent I, 4 parts of carboxylated metal organic framework material, 5 parts of silane coupling agent, 0.4 part of antioxidant and 0.4 part of ester exchange inhibitor;
(2) uniformly mixing graphite powder, carbon nano tubes and a silane coupling agent, performing ball milling at 4 ℃ for 20min, adding dimethylbenzene, a carboxylated metal organic framework material and a dispersing agent I which are 4 times of the total weight of the graphite powder and the carbon nano tubes, and performing ultrasonic dispersion for 30 min; then adding amino modified polyphenylene sulfide, polybutylene terephthalate, an antioxidant and an ester exchange inhibitor, heating to 200 ℃, refluxing and stirring for 10min, continuously stirring to remove xylene, and then transferring to an internal mixer for mixing for 60min, wherein the internal mixing temperature is controlled at 290 ℃;
(3) and (3) transferring the banburying product obtained in the step (2) to a double-screw extruder for extrusion granulation to obtain master batches for engineering plastics.
Example 4
The master batch for the engineering plastics comprises the following raw materials in parts by weight: 80 parts of amino modified polyphenylene sulfide, 50 parts of polybutylene terephthalate, 80 parts of graphite powder, 16 parts of carbon nano tube, 15 parts of dispersing agent II, 3 parts of carboxylated metal organic framework material, 4 parts of silane coupling agent, 0.3 part of antioxidant and 0.2 part of ester exchange inhibitor;
the number average molecular weight of the amino modified polyphenylene sulfide is 17000 g/mol; the polybutylene terephthalate has a number average molecular weight of 24000g/mol,
the graphite powder is formed by mixing graphite powder A with the particle size of 300nm and graphite powder B with the particle size of 1 mu m according to the weight ratio of 5: 1; the diameter of the outer tube of the carbon nano tube is 30nm, and the length of the outer tube is 2 mu m; the silane coupling agent is selected from gamma-methacryloxypropyltrimethoxysilane; the antioxidant is selected from dilauryl thiodipropionate; the ester exchange inhibitor is selected from sodium dihydrogen phosphate.
The preparation method of the master batch for the engineering plastics comprises the following steps:
(1) weighing the following raw materials, by weight, 80 parts of amino modified polyphenylene sulfide, 50 parts of polybutylene terephthalate, 80 parts of graphite powder, 16 parts of carbon nano tube, 15 parts of dispersing agent II, 3 parts of carboxylated metal organic framework material, 4 parts of silane coupling agent, 0.3 part of antioxidant and 0.2 part of ester exchange inhibitor;
(2) uniformly mixing graphite powder, carbon nano tubes and a silane coupling agent, performing ball milling at 0 ℃ for 15min, adding dimethylbenzene, a carboxylated metal organic framework material and a dispersing agent II which are 5 times of the total weight of the graphite powder and the carbon nano tubes, and performing ultrasonic dispersion for 40 min; then adding amino modified polyphenylene sulfide, polybutylene terephthalate, an antioxidant and an ester exchange inhibitor, heating to 190 ℃, refluxing and stirring for 15min, continuously stirring to remove xylene, then transferring to an internal mixer for mixing for 50min, and controlling the internal mixing temperature at 295 ℃;
(3) and (3) transferring the banburying product obtained in the step (2) to a double-screw extruder for extrusion granulation to obtain master batches for engineering plastics.
Comparative example 1
The polybutylene terephthalate was not added, the amount of the amino-modified polyphenylene sulfide was adjusted to 150 parts, and the remaining components and the preparation method were completely the same as in example 1.
Comparative example 2
The remainder of the components and the preparation process were completely identical to those of example 1, without addition of a carboxylated metal-organic framework material.
Comparative example 3
The graphite powder is composed of graphite powder A with the particle size of 200nm, graphite powder B with the particle size of 1 mu m is not contained, and the rest components and the preparation method are completely consistent with those of the embodiment 1.
Comparative example 4
The carbon nanotube was not contained, the amount of graphite powder was adjusted to 95 parts, and the remaining components and the preparation method were completely identical to those of example 1.
2. Performance testing
The master batches for engineering plastics prepared in examples 1 to 4 and comparative examples 1 to 4 were added to polyphenylene sulfide resin (with a data molecular weight of 20000g/mol) at an amount of 5%, molded by an injection molding machine to obtain test specimens, and the specimens were stabilized at 23 ℃ and 50% humidity for 24 hours to test surface resistivity and mechanical properties, and the test results are shown in table 1.
TABLE 1
From the test data in table 1, it can be found that the master batch for engineering plastics, which has both conductivity and mechanical properties, is prepared by the invention, and the carbon-based conductive filler can be well dispersed in a resin matrix consisting of amino modified polyphenylene sulfide and polybutylene terephthalate to form a better conductive network; and the mechanical property of the material is maintained by selecting the components, particularly adding a specific dispersant and a carboxylated metal organic framework material.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The master batch for engineering plastics is characterized in that: the composite material comprises the following raw materials in parts by weight:
80-100 parts of amino modified polyphenylene sulfide, 30-50 parts of polybutylene terephthalate, 80-100 parts of graphite powder, 10-20 parts of carbon nano tube, 10-15 parts of dispersing agent, 3-6 parts of carboxylated metal organic framework material, 3-6 parts of silane coupling agent, 0.2-0.5 part of antioxidant and 0.1-0.5 part of ester exchange inhibitor;
the dispersing agent is amino modified polyester resin, and the weight average molecular weight is 6000g/mol 5000-6000 g/mol; the preparation method of the dispersant comprises the following steps:
(1) weighing the following raw materials in parts by weight: 5-10 parts of polyether glycol, 15-25 parts of adipic acid, 30-50 parts of terephthalic acid, 10-20 parts of butanediol, 12-18 parts of hexanediol, 3-5 parts of neopentyl glycol, 3-5 parts of dimethylolpropionic acid, 20-30 parts of diphenylmethane diisocyanate, 30-50 parts of tetraethylenepentamine, 0.02-0.05 part of tetrabutyl titanate and 80-100 parts of dimethylbenzene;
(2) sequentially adding polyether dihydric alcohol, adipic acid, terephthalic acid, butanediol, hexanediol, neopentyl glycol, tetrabutyl titanate and half of xylene into a reaction container, introducing nitrogen, heating to 180 +/-10 ℃, carrying out heat preservation reaction for 12-15h, and continuously removing moisture through a water separator in the reaction process; adding dimethylolpropionic acid, continuously heating to 200 +/-10 ℃, reacting for 6-8h, and after the reaction is finished, carrying out reduced pressure distillation to remove xylene and unreacted micromolecules to obtain polyether modified polyester;
(3) mixing the polyether modified polyester prepared in the step (2), diphenylmethane diisocyanate and the rest xylene, adding the mixture into a reaction vessel, introducing nitrogen, heating to 50 +/-2 ℃, and reacting for 2-4 h; finally, adding tetraethylenepentamine, heating to 70 +/-2 ℃, reacting for 2-3h, and distilling under reduced pressure to remove xylene and unreacted micromolecules to obtain a dispersing agent;
the number average molecular weight of the polyether glycol in the preparation method of the dispersant is 200-300 g/mol; the number average molecular weight of the amino modified polyphenylene sulfide is 15000-20000 g/mol; the number average molecular weight of the polybutylene terephthalate is 20000-30000 g/mol; the graphite powder is formed by mixing 100-300nm graphite powder A and 1-3 mu m graphite powder B according to the weight ratio of 5-7: 1.
2. The master batch for engineering plastics according to claim 1, which is characterized in that: the diameter of the outer tube of the carbon nano tube is 10-50nm, and the length of the outer tube is 1-3 mu m.
3. The master batch for engineering plastics according to claim 2, wherein: and oxidizing the surface of the graphite powder or the carbon nano tube to graft a carboxyl functional group on the surface.
4. The master batch for engineering plastics according to claim 1, wherein the master batch comprises: the silane coupling agent is at least one selected from gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane.
5. The master batch for engineering plastics according to claim 1, wherein the master batch comprises: the antioxidant is at least one selected from phenolic antioxidants, phosphite antioxidants and sulfur-containing ester antioxidants.
6. The master batch for engineering plastics according to claim 5, wherein the master batch comprises: the antioxidant is selected from at least one of 2, 6-di-tert-butylphenol, 2, 6-di-tert-butyl-4-ethylphenol, 4-hydroxymethyl-2, 6-di-tert-butylphenol, 2, 6-di-tert-butyl-4-n-butylphenol, triphenyl phosphite, tris (nonylphenyl) phosphite, triisooctyl phosphite, triisodecyl phosphite, diisodecyl phosphite, dilauryl thiodipropionate and distearyl thiodipropionate.
7. The master batch for engineering plastics according to claim 1, which is characterized in that: the ester exchange inhibitor is at least one selected from sodium dihydrogen phosphate, sodium hexametaphosphate and ammonium hypophosphite.
8. The master batch for engineering plastics according to claim 1, which is characterized in that: the composite material comprises the following raw materials in parts by weight: 100 parts of amino modified polyphenylene sulfide, 50 parts of polybutylene terephthalate, 80 parts of graphite powder, 15 parts of carbon nano tube, 13 parts of dispersing agent, 5 parts of carboxylated metal organic framework material, 6 parts of silane coupling agent, 0.5 part of antioxidant and 0.3 part of ester exchange inhibitor.
9. The method for preparing the master batch for the engineering plastic, according to claims 1-8, is characterized in that: the method comprises the following steps:
(1) weighing 80-100 parts of amino modified polyphenylene sulfide, 30-50 parts of polybutylene terephthalate, 80-100 parts of graphite powder, 10-20 parts of carbon nano tube, 10-15 parts of dispersing agent, 3-6 parts of carboxylated metal organic framework material, 3-6 parts of silane coupling agent, 0.2-0.5 part of antioxidant and 0.1-0.5 part of ester exchange inhibitor according to parts by weight;
(2) uniformly mixing graphite powder, carbon nanotubes and a silane coupling agent, performing ball milling at 0-5 ℃ for 10-20min, adding dimethylbenzene, a carboxylated metal organic framework material and a dispersing agent which are 3-5 times of the total weight of the graphite powder and the carbon nanotubes, and performing ultrasonic dispersion for 20-40 min; then adding amino modified polyphenylene sulfide, polybutylene terephthalate, an antioxidant and an ester exchange inhibitor, heating to 180 ℃ and 200 ℃, refluxing and stirring for 10-20min, continuously stirring to remove xylene, then transferring to an internal mixer for mixing for 40-60min, and controlling the mixing temperature at 290 ℃ and 300 ℃;
(3) and (3) transferring the banburying product obtained in the step (2) to a double-screw extruder for extrusion granulation to obtain master batches for engineering plastics.
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