CN113121995A

CN113121995A - Nylon composite material with wear-resisting and antistatic properties as well as preparation method and application thereof

Info

Publication number: CN113121995A
Application number: CN202110419361.XA
Authority: CN
Inventors: 王根林; 吴健; 史青; 丁克鸿; 徐林; 聂庆超; 徐志斌; 卞辰超; 王浩; 冯青宇
Original assignee: Jiangsu Yangnong Chemical Group Co Ltd
Current assignee: Jiangsu Yangnong Chemical Group Co Ltd
Priority date: 2021-04-19
Filing date: 2021-04-19
Publication date: 2021-07-16

Abstract

The invention provides a nylon composite material with wear-resisting and antistatic properties, a preparation method and application thereof, wherein the nylon composite material comprises nylon and an additive component; the additive components comprise ultra-high molecular weight polyethylene and carbon nano tubes; the mass ratio of the ultra-high molecular weight polyethylene to the nylon is 0.05-0.3: 1; the nylon composite material has excellent friction resistance and antistatic property, and can be used for manufacturing automobile parts and shuttles in looms; and the preparation method of the nylon composite material is simple and easy for industrial operation.

Description

Nylon composite material with wear-resisting and antistatic properties as well as preparation method and application thereof

Technical Field

The invention relates to the technical field of functional composite materials, in particular to a nylon composite material with wear resistance and antistatic performance and a preparation method and application thereof.

Background

The nylon is a general engineering plastic with high mechanical strength, corrosion resistance and moderate price, has simple forming process, and can replace metal to be used for manufacturing parts in industries such as automobiles, electronic appliances and the like. However, a large number of amido bonds exist in a nylon molecular chain, the polarity is high, when the nylon molecular chain is rubbed with materials such as metal, an adhesion phenomenon is easily generated on the surface of the metal material, meanwhile, the nylon surface resistivity is high, the antistatic property is poor, and static electricity is easily accumulated in the using process to bring potential safety hazards. The wear-resistant and antistatic nylon material prepared by improving the friction and the electrical property can be used for manufacturing rolling bearings, engine blades, shuttles of weaving machines and the like.

Currently, the antistatic performance of polyamide materials is improved, and the most common method is to add conductive filler antistatic agents, such as metal fibers, carbon black, carbon nanotubes and the like. However, the application of the metal fiber and the carbon fiber is restricted due to the defects of high addition amount, high price and the like; the problems of the reduction of the physical and mechanical properties, the reduction of the fluidity and the like of the nylon resin are easily caused by the fact that the carbon black needs to be added in a large amount due to low conductive efficiency. The method for improving the friction performance of the polyamide material mainly comprises inorganic particle filling modification, fiber reinforcement modification, inorganic particle/fiber blending modification, resin blending modification and surface modification. The inorganic particle and fiber modification method has the problem of poor compatibility of the filler and the resin matrix, and the friction and mechanical properties of the composite material are negatively affected when the filling amount is too large; the surface modification method injects ions into the surface of the polymer, so that the improvement effect is not obvious and the cost is high.

CN107216651A discloses a toughened antistatic PA66 composition, wherein the PA66 composition is composed of the following components in parts by weight: 50-80 parts of nylon 66 slices, 10-20 parts of polypropylene, 1-10 parts of maleic anhydride grafted PP, 10-30 parts of glass fiber, 5-10 parts of large-particle-size nickel powder, 5-10 parts of small-particle-size nickel powder, 0.5-3 parts of silane coupling agent and 0.5-2 parts of antioxidant; 0.5-2 parts of lubricant, and the product has the performances of wear resistance, good tensile strength and the like and also has antistatic performance.

CN110240801A discloses a high-performance carbon fiber reinforced nylon composite material and a preparation method thereof, wherein the high-performance carbon fiber reinforced nylon composite material is composed of 50-70 wt% of nylon resin, 18-30 wt% of long carbon fiber, 2-6 wt% of compatilizer, 3-7 wt% of filling graphite, 2-5 wt% of organic sepiolite, 1-3 wt% of flame retardant and 1-2 wt% of other antistatic agents, and the obtained composite material has excellent mechanical property, wear resistance, flame retardance and antistatic property.

CN102731994A discloses a nylon composite material, a preparation method, an application thereof and a plastic product of the nylon composite material, wherein the nylon composite material comprises the following main components: the high-temperature nylon comprises high-temperature nylon, a nano conductive material, a lubricant, a surface treating agent and an antioxidant, wherein the high-temperature nylon comprises the following components in parts by weight: 70-95 parts of nylon; 3-25 parts of nano conductive material; 0.1-3 parts of a lubricant; 0.1-1.8 parts of surface treating agent; 0.3-3.5 parts of antioxidant; and 0.5-2.8 parts of a compatilizer; wherein the high-temperature nylon can be replaced by 0-8 parts by weight of common nylon.

However, the methods have the problems that the added antistatic agent is too much, the dispersion is difficult, the mechanical property of nylon is reduced along with the increase of the dosage, and meanwhile, the melt flowability is poor and the processing is difficult.

Therefore, it is highly desirable to develop a nylon composite material with wear resistance and antistatic property, which is easy to process, and a preparation method thereof.

Disclosure of Invention

In order to solve the technical problems, the invention provides a nylon composite material with wear resistance and antistatic property, and a preparation method and application thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides a nylon composite material with wear resistance and antistatic performance, wherein the nylon composite material comprises components of nylon and an additive component; the additive components comprise ultra-high molecular weight polyethylene and carbon nano tubes; the mass ratio of the ultra-high molecular weight polyethylene to the nylon is 0.05-0.3: 1.

In the nylon composite material, the ultra-high molecular weight polyethylene can be distributed in a nylon matrix, the composite material is in a sea-island structure, and island phase ultra-high molecular weight polyethylene, namely UHMWPE, is easier to form an interface film on a sliding interface during friction; the invention forms the nanometer transfer film which integrates the characteristics of low friction coefficient of UHMWPE and solid lubricity of the carbon nano tube, so that the nylon composite material has excellent high wear resistance. Moreover, the carbon nano tube is of a tubular structure and can play a role of a micro bearing in a friction interface, and the damaged carbon nano tube can fill micro scratches on the surface of the friction pair, so that the friction factor is reduced, and the abrasion is reduced. In addition, the addition of the carbon nano tube endows the composite material with an antistatic function, and the application field of the composite material is enlarged; the composite material has excellent processing performance and is easy to be molded by injection and extrusion.

The mass ratio of the ultra-high-molecular-weight polyethylene to the nylon in the present invention is 0.05 to 0.3:1, and may be, for example, 0.05:1, 0.08:1, 0.11:1, 0.14:1, 0.17:1, 0.19:1, 0.22:1, 0.25:1, 0.28:1 or 0.3:1, but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are also applicable.

The nylon composite material strictly controls the mass ratio of the ultra-high molecular weight polyethylene to the nylon at 0.05-0.3: 1, is more favorable for forming a ternary nano interface film, and improves the wear resistance of the nylon composite material.

Preferably, the mass ratio of the carbon nanotubes to nylon is 0.01 to 0.03:1, for example, 0.01:1, 0.013:1, 0.015:1, 0.017:1, 0.019:1, 0.022:1, 0.024:1, 0.026:1, 0.028:1, or 0.03:1, but not limited to the above-mentioned values, and other values not listed in the above range are also applicable.

The carbon nano tube has low addition amount, can simultaneously ensure the antistatic performance, has good dispersion in nylon and ultra-high molecular weight polyethylene, and also has excellent processing performance.

Preferably, the carbon nanotubes are surfactant modified carbon nanotubes.

Preferably, the surfactant comprises an anionic surfactant and/or a cationic surfactant.

Preferably, the carbon nanotube is a carbon nanotube modified with an anionic surfactant and a cationic surfactant in this order.

Preferably, the anionic surfactant has a benzene ring structure.

The invention adopts the anionic surfactant with benzene ring, utilizes pi-pi interaction to lead the surface of the carbon nano tube to have more negative charges, and is beneficial to better adsorbing the cationic surfactant on the surface of the carbon nano tube. The surface modification of the carbon nano tube is carried out by adopting the combination of the anionic surfactant and the cationic surfactant, so that the carbon long chain is adsorbed and arranged on the surface of the carbon nano tube, the affinity of the carbon nano tube and matrix resin is improved, and the modified carbon nano tube is easily dispersed in a polymer matrix.

The invention utilizes a non-covalent method to carry out surface modification on the carbon nano tube, which is realized by a surfactant, and the sp2 hybrid structure of the carbon nano tube can be reserved.

Preferably, the anionic surfactant is negatively charged.

Preferably, the anionic surfactant comprises any one of or a combination of at least two of sodium N, N-didodecyl-2, 6-pyridinedicarboxamide propionate, N ' - (sodium dodecyldi-p-benzenesulfonate) ethylenediamine or di-linear alkyldiphenylmethane disulfonate, typical but non-limiting combinations being a combination of sodium N, N-didodecyl-2, 6-pyridinedicarboxamide propionate and N, N ' - (sodium dodecyldi-p-benzenesulfonate) ethylenediamine, a combination of N, N ' - (sodium dodecyldi-p-benzenesulfonate) ethylenediamine and di-linear alkyldiphenylmethane disulfonate, a combination of sodium N, N-didodecyl-2, 6-pyridinedicarboxamide propionate and di-linear alkyldiphenylmethane disulfonate.

Preferably, the cationic surfactant comprises any one of or a combination of at least two of tetrabutylammonium chloride, cetyltrimethylammonium chloride or cetyltrimethylammonium bromide, typical but not limiting combinations being combinations of tetrabutylammonium chloride and cetyltrimethylammonium chloride, cetyltrimethylammonium bromide and cetyltrimethylammonium chloride, and combinations of tetrabutylammonium chloride and cetyltrimethylammonium bromide.

Preferably, the carbon nanotubes are multi-walled carbon nanotubes.

The invention preferably adopts the multi-wall carbon nano tube, the industrial preparation process is mature compared with the single-wall carbon nano tube, the cost is lower than that of the single-wall carbon nano tube, and the preparation cost of the composite material can be reduced.

The carbon nanotubes preferably have a diameter of 10 to 15nm, and may be, for example, 10nm, 10.6nm, 11.2nm, 11.7nm, 12.3nm, 12.8nm, 13.4nm, 13.9nm, 14.5nm or 15nm, but not limited to the above-mentioned values, and other values not listed in this range are also applicable.

The carbon nanotubes preferably have a length of 10 to 30 μm, and may be, for example, 10 μm, 13 μm, 15 μm, 17 μm, 19 μm, 22 μm, 24 μm, 26 μm, 28 μm or 30 μm, but are not limited to the above-mentioned values, and other values not listed in the above range are also applicable.

Preferably, the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 300 to 400 ten thousand, for example, 300 ten thousand, 312 ten thousand, 323 ten thousand, 334 ten thousand, 345 ten thousand, 356 ten thousand, 367 ten thousand, 378 ten thousand, 389 ten thousand, or 400 ten thousand, etc., but is not limited to the above-mentioned values, and other values not mentioned in the range are also applicable.

Preferably, the particle size of the ultra-high molecular weight polyethylene is 120 to 200 mesh, for example, 120 mesh, 129 mesh, 138 mesh, 147 mesh, 156 mesh, 165 mesh, 174 mesh, 183 mesh, 192 mesh or 200 mesh, etc., but not limited to the recited values, and other values not recited in the range are also applicable.

Preferably, the bulk density of the ultra-high molecular weight polyethylene is 0.4-0.5 g/cm³For example, it may be 0.4g/cm³、0.42g/cm³、0.43g/cm³、0.44g/cm³、0.45g/cm³、0.46g/cm³、0.47g/cm³、0.48g/cm³、0.49g/cm³Or 0.5g/cm³And the like, but are not limited to the recited values, and other values not recited within the range are equally applicable.

Preferably, the nylon has a relative viscosity of 2.3 to 3.2, and may be, for example, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1 or 3.2, but not limited to the values listed, and other values not listed in this range are also applicable.

The relative viscosity in the present invention refers to the viscosity with respect to water.

Preferably, the nylon comprises nylon chips.

The specific type of nylon is not particularly limited in the present invention, and nylon materials commonly used by those skilled in the art can be used, for example, any one or a combination of at least two of the conventional nylon materials such as nylon 6, nylon 66 or nylon 1010 can be included, wherein typical but non-limiting combinations are a combination of nylon 6 and nylon 66, a combination of nylon 66 and nylon 1010, and a combination of nylon 6 and nylon 1010.

Preferably, the content of the ultra-high molecular weight polyethylene in the nylon composite is 5 to 20%, for example, 5%, 7%, 9%, 10%, 12%, 14%, 15%, 17%, 19%, or 20%, etc., but is not limited to the recited values, and other values not recited in this range are also applicable.

Preferably, the content of the carbon nanotubes in the nylon composite material is 1 to 2%, for example, 1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, etc., but not limited to the recited values, and other values not recited in this range are also applicable.

Preferably, the nylon content in the nylon composite material is 75 to 90%, for example, 75%, 77%, 79%, 80%, 82%, 84%, 85%, 87%, 89%, or 90%, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.

Preferably, the nylon composite further comprises an antioxidant and an interfacial compatibilizer.

The antioxidant of the present invention is not particularly limited, and any antioxidant used in the art may be used, and for example, any one or a combination of at least two of conventional antioxidants such as antioxidant 1010, antioxidant 168, antioxidant 1098, antioxidant 1620, and antioxidant 626 may be included, wherein typical but non-limiting combinations are a combination of antioxidant 1010 and antioxidant 168, a combination of antioxidant 1098 and antioxidant 168, and a combination of antioxidant 1620 and antioxidant 626.

The interfacial compatibilizer used in the present invention is not particularly limited, and may be an interfacial compatibilizer used in the art, and for example, may include any one or a combination of at least two of maleic anhydride grafted polyolefin, maleic anhydride grafted polyolefin elastomer, and maleic anhydride grafted SEBS, where typical but non-limiting combinations are a combination of maleic anhydride grafted polyolefin and maleic anhydride grafted polyolefin elastomer, and a combination of maleic anhydride grafted polyolefin elastomer and maleic anhydride grafted SEBS.

Preferably, the content of the antioxidant in the nylon composite material is 0.3 to 1.0%, and may be, for example, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.75%, 0.8%, 0.9%, 0.95%, or 1.0%, etc., but is not limited to the enumerated values, and other values not enumerated within this range are also applicable.

Preferably, the content of the interfacial compatibilizer in the nylon composite is 0.3 to 1.0%, and for example, may be 0.3%, 0.4%, 0.55%, 0.6%, 0.7%, 0.75%, 0.8%, 0.9%, 0.95%, or 1.0%, etc., but is not limited to the values listed, and other values not listed in this range are also applicable.

Preferably, the preparation method comprises: mixing the components of the nylon composite material, and sequentially carrying out melt mixing and extrusion granulation to obtain the nylon composite particles.

Preferably, the mixing is carried out in a mixer.

The temperature and stirring speed of the mixing are not particularly limited in the present invention, and those known to those skilled in the art can be used, for example, the temperature of the mixing is normal temperature. For example, the stirring speed of the mixing is 1300r/min or the like.

Preferably, the melt-kneading temperature is 220 to 275 ℃, for example, 220 ℃, 227 ℃, 233 ℃, 239 ℃, 245 ℃, 251 ℃, 257 ℃, 263 ℃, 269 ℃, or 275 ℃, but not limited to the above-mentioned values, and other values not shown in the above range are also applicable.

Preferably, the feeding speed of the extrusion granulation is 18 to 25rps, for example, 18rps, 19rps, 20rps, 21rps, 22rps, 23rps, 24rps, 25rps or 25rps, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.

Preferably, the melt-kneading and extrusion-pelletizing are carried out using a twin-screw extruder.

Preferably, the twin-screw extruder is temperature-controlled in zones.

Preferably, the zone temperature control comprises at least three zone separate temperature control.

Preferably, the temperature control in the subareas comprises the temperature of 200-250 ℃ in the first area, 230-265 ℃ in the second area, 230-270 ℃ in the third area, 230-280 ℃ in the fourth area, 230-280 ℃ in the fifth area, 240-280 ℃ in the sixth area, 240-280 ℃ in the seventh area, 240-280 ℃ in the eighth area and 240-280 ℃ in the ninth area.

In the present invention, the temperature of the first zone is 200 to 250 ℃, for example, 200 ℃, 215 ℃, 220 ℃, 235 ℃, 245 ℃ or 250 ℃, but not limited to the values listed, and other values not listed in the range are also applicable.

The temperature of the second zone is 230 to 265 ℃ and may be, for example, 230 ℃, 235 ℃, 240 ℃, 245 ℃, 250 ℃, 252 ℃, 255 ℃, 257 ℃, 260 ℃ or 265 ℃, but is not limited to the values listed, and other values not listed in the range are also applicable.

The temperature of the three zones is 230 to 270 ℃, and may be, for example, 230 ℃, 240 ℃, 245 ℃, 250 ℃, 252 ℃, 255 ℃, 260 ℃, 265 ℃ or 270 ℃, but is not limited to the values listed, and other values not listed in the range are also applicable.

The temperature in the fourth zone is 230 to 280 ℃ and may be, for example, 230 ℃, 240 ℃, 245 ℃, 250 ℃, 255 ℃, 265 ℃, 270 ℃, 273 ℃, 276 ℃ or 280 ℃, but is not limited to the values listed, and other values not listed in the range are also applicable.

The temperature of the fifth zone is 230 to 280 ℃, and may be, for example, 230 ℃, 240 ℃, 245 ℃, 250 ℃, 255 ℃, 260 ℃, 270 ℃, 273 ℃, 276 ℃ or 280 ℃, but is not limited to the values listed, and other values not listed in the range are also applicable.

The temperature of the sixth zone is 240 to 280 ℃, and may be, for example, 240 ℃, 250 ℃, 255 ℃, 260 ℃, 263 ℃, 265 ℃, 270 ℃, 275 ℃ or 280 ℃, but is not limited to the values listed, and other values not listed in the range are also applicable.

The temperature in the seventh zone is 240 to 280 ℃, and may be, for example, 240 ℃, 250 ℃, 253 ℃, 255 ℃, 259 ℃, 265 ℃, 270 ℃, 277 ℃ or 280 ℃, but is not limited to the values listed, and other values not listed in the range are also applicable.

The temperature of the eight zones is 240 to 280 ℃, and may be, for example, 240 ℃, 245 ℃, 250 ℃, 255 ℃, 265 ℃, 269 ℃, 272 ℃, 275 ℃, 279 ℃, or 280 ℃, but is not limited to the values listed, and other values not listed in the range are also applicable.

The nine-zone temperature is 240 to 280 ℃, and may be, for example, 240 ℃, 245 ℃, 252 ℃, 255 ℃, 260 ℃, 263 ℃, 267 ℃, 272 ℃, 276 ℃ or 280 ℃, but is not limited to the values listed, and other values not listed in the range are also applicable.

Preferably, the twin-screw extruder has a rotational speed of 30 to 38rps, and may be, for example, 30rps, 31rps, 32rps, 33rps, 34rps, 35rps, 36rps, 37rps or 38rps, but is not limited to the values listed, and other values not listed in this range are also applicable.

Preferably, the mixing further comprises a modification of the carbon nanotubes.

Preferably, the modification of the carbon nanotubes comprises: dispersing the carbon nano tube in a surfactant, and separating to obtain the modified carbon nano tube.

Preferably, the modification of the carbon nanotubes comprises: mixing the carbon nano tube and the anionic surfactant, and performing first dispersion and first separation to obtain a first material. And mixing the first material and the cationic surfactant, and performing second dispersion and second separation to obtain the modified carbon nanotube.

The dispersing means of the first dispersion and the second dispersion in the present invention is not particularly limited, and may include any one or a combination of at least two of the conventional dispersing methods such as ultrasonic treatment, high energy ball milling, and high speed dispersion, and typical but non-limiting combinations thereof include a combination of ultrasonic treatment and high energy ball milling, a combination of high energy ball milling and high speed dispersion, and a combination of ultrasonic treatment and high speed dispersion.

The first separation step and the second separation step are not particularly limited, and may include any one or a combination of at least two of the conventional separation methods such as centrifugation, suction filtration, or filtration, wherein typical but non-limiting combinations include a combination of centrifugation and suction filtration, a combination of suction filtration and filtration, and a combination of centrifugation and filtration.

Preferably, the anionic surfactant accounts for 0.1 to 1% by mass of the carbon nanotube, and may be, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%, but is not limited to the above-mentioned values, and other values not listed in the range are also applicable.

Preferably, the cationic surfactant accounts for 0.1 to 1% by mass of the carbon nanotube, and may be, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%, but is not limited to the above-mentioned values, and other values not listed in the above range are also applicable.

Preferably, the nylon composite particles are dried and injection molded in sequence to obtain the nylon composite material.

The present invention has no special requirements for the drying temperature and mode, and any temperature and mode which can be used for drying and is well known to those skilled in the art can be adopted.

The present invention also does not require any particular means for injection molding, and any means known to those skilled in the art that can be used for injection molding may be used.

In a third aspect, the invention provides the use of the nylon composite material with wear resistance and antistatic performance in automobile parts or weaving machines.

The nylon composite material provided by the invention is wear-resistant and antistatic, and can be well applied to automobile parts or looms.

Preferably, the nylon composite is used in a rolling bearing or an engine blade.

Preferably, the use of the nylon composite in a loom shuttle.

Compared with the prior art, the invention has at least the following beneficial effects:

(1) the nylon composite material provided by the invention has excellent mechanical properties, and under the better condition, the tensile strength is more than 77MPa, the bending strength is more than 104MPa, and the impact strength is more than 59 MPa;

(2) the nylon composite material provided by the invention has excellent wear resistance, under the better condition, the friction coefficient is less than or equal to 0.289, the abrasion is less than or equal to 2.8mg, and the nylon composite material has excellent antistatic performance, the volume resistivity is less than or equal to 2.23 multiplied by 10⁸Ω·cm；

(3) The preparation method of the nylon composite material provided by the invention has the advantages of simple process, easiness in molding preparation, good melt fluidity, no blocky phenomenon, no air bubbles and the like.

Detailed Description

For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

First, an embodiment

Preparation of carbon nanotubes

Carbon nanotube A

The preparation method of the carbon nano tube A comprises the following steps:

(1) adding 2g of purchased multi-walled carbon nano-tube with a negatively charged surface, 0.01g of double linear alkyl diphenylmethane disulfonate (DSDM) and 300g of deionized water into a 500ml beaker, and performing first dispersion by using an ultrasonic cell crusher (150W) through ultrasonic waves; keeping the mixed solution to be cooled by using an ice water bath, stopping for 3 seconds every 3 seconds of ultrasonic treatment, and continuing for 1 hour to obtain a first mixed solution; then centrifuging the first mixed solution for first separation, and washing for 2 times by using deionized water to obtain a first material; the pipe diameter of the carbon nano tube is 15nm, and the length of the carbon nano tube is 20 mu m;

(2) and (2) adding the first material obtained in the step (1), 0.0144g of hexadecyl trimethyl ammonium bromide (CTAB) and 300g of deionized water into a 500ml round-bottom flask, stirring for 1h, performing second dispersion, centrifuging for performing second separation, washing for 2 times by using the deionized water, and finally performing freeze drying to obtain the modified carbon nanotube.

Carbon nanotube B

The preparation method of the carbon nano tube B comprises the following steps:

(1) adding 2g of purchased multi-walled carbon nano-tube with a negative surface, 0.02g of N, N' - (dodecyl sodium di-p-benzenesulfonate) ethylenediamine and 300g of deionized water into a 500ml beaker, and performing first dispersion by using an ultrasonic cell crusher (150W) through ultrasonic waves; keeping the mixed solution to be cooled by using an ice water bath, stopping for 3 seconds every 3 seconds of ultrasonic treatment, and continuing for 1 hour to obtain a first mixed solution; then centrifuging the first mixed solution for first separation, and washing for 2 times by using deionized water to obtain a first material; the pipe diameter of the carbon nano tube is 10nm, and the length of the carbon nano tube is 30 mu m;

(2) and (2) adding the first material obtained in the step (1), 0.02g of tetrabutylammonium chloride and 300g of deionized water into a 500ml round-bottom flask, stirring for 1h, performing second dispersion, centrifuging for second separation, washing for 2 times by using deionized water, and finally performing freeze drying to obtain the modified carbon nanotube.

Carbon nanotube C

The preparation method of the carbon nano tube C comprises the following steps:

(1) adding 2g of purchased multi-walled carbon nano-tube with negative charges on the surface, 0.002g of N, N-didodecyl-2, 6-pyridinediamide sodium propionate and 300g of deionized water into a 1000ml beaker, and performing first dispersion by using an ultrasonic cell crusher (150W) through ultrasound; keeping the mixed solution to be cooled by using an ice water bath, stopping for 3 seconds every 3 seconds of ultrasonic treatment, and continuing for 1 hour to obtain a first mixed solution; then centrifuging the first mixed solution for first separation, and washing for 2 times by using deionized water to obtain a first material; the pipe diameter of the carbon nano tube is 12nm, and the length of the carbon nano tube is 10 mu m;

(2) and (2) adding the first material obtained in the step (1), 0.002g of hexadecyltrimethylammonium chloride and 300g of deionized water into a 500ml round-bottom flask, stirring for 1h, performing second dispersion, centrifuging, performing second separation, washing for 2 times by using deionized water, and finally performing freeze drying to obtain the modified carbon nanotube.

In the modification process of the carbon nanotube, the operation parameters of the ultrasonic cell crusher are not particularly limited, and the skilled person can select the operation parameters according to the actual process conditions. The time for the second dispersion of the subsequent stirring is not particularly limited, and can be adjusted according to actual conditions.

Example 1

The embodiment provides a nylon composite material with wear resistance and antistatic property, and the nylon composite material comprises the following components in percentage by mass:

the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 300 ten thousand, the granularity is 120 meshes, and the bulk density is 0.46g/cm³(ii) a Relative of the nylonThe viscosity was 2.7.

The embodiment also provides a preparation method of the nylon composite material with wear resistance and antistatic property, and the preparation method comprises the following steps:

firstly, adding the raw materials into a mixer in full quantity for mechanical mixing at 1300r/min, then adding the uniformly mixed materials into a double-screw extruder for melt mixing and extrusion granulation; and (3) placing the extruded granules in an oven at 80 ℃ for 12h, and then performing injection molding by using an injection molding machine.

Wherein the parameters of the double-screw extruder are as follows: the temperature of a first area is 230 ℃, the temperature of a second area is 255 ℃, the temperature of a third area is 255 ℃, the temperature of a fourth area is 260 ℃, the temperature of a fifth area is 260 ℃, the temperature of a sixth area is 265 ℃, the temperature of a seventh area is 260 ℃, the temperature of an eighth area is 265 ℃ and the temperature of a ninth area is 255 ℃; the feed rate was 22rps and the rotational speed was 35 rps.

Example 2

the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 300 ten thousand, the granularity is 120 meshes, and the bulk density is 0.46g/cm³(ii) a The relative viscosity of the nylon was 2.7.

The preparation method of the nylon composite material with wear resistance and antistatic performance in this example is the same as that in example 1.

Example 3

Example 4

the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 400 ten thousand, the granularity is 200 meshes, and the bulk density is 0.5g/cm³(ii) a The relative viscosity of the nylon was 2.3.

firstly, adding the raw materials into a mixer in full quantity for mechanical mixing at 1300r/min, then adding the uniformly mixed materials into a double-screw extruder for melt mixing and extrusion granulation; and (3) placing the extruded granules in a 90 ℃ oven for 2h, and then performing injection molding by using an injection molding machine.

Wherein the parameters of the double-screw extruder are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 235 ℃, the temperature of the third zone is 240 ℃, the temperature of the fourth zone is 245 ℃, the temperature of the fifth zone is 250 ℃, the temperature of the sixth zone is 245 ℃, the temperature of the seventh zone is 245 ℃, the temperature of the eighth zone is 245 ℃ and the temperature of the ninth zone is 245 ℃; the feed rate was 18rps and the rotational speed was 38 rps.

Example 5

the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 350 ten thousand, the granularity is 120 meshes, and the bulk density is 0.4g/cm³(ii) a The relative viscosity of the nylon was 3.2.

Wherein the parameters of the double-screw extruder are as follows: the temperature of the first zone is 230 ℃, the temperature of the second zone is 235 ℃, the temperature of the third zone is 240 ℃, the temperature of the fourth zone is 240 ℃, the temperature of the fifth zone is 240 ℃, the temperature of the sixth zone is 245 ℃, the temperature of the seventh zone is 245 ℃, the temperature of the eighth zone is 245 ℃, and the temperature of the ninth zone is 245 ℃; the feed rate was 25rps and the rotational speed was 30 rps.

Example 6

The embodiment provides a nylon composite material with wear resistance and antistatic performance, which is prepared by modifying the component proportion of the nylon composite material into 750g of nylon 66 slices; the carbon nanotube A30g was the same as in example 1 except that the contents of the remaining components were unchanged.

Example 7

The embodiment provides a nylon composite material with wear resistance and antistatic performance, which is prepared by modifying the component ratio of nylon 66 slices to 775 g; the carbon nanotubes A5g were the same as in example 1 except that the contents of the remaining components were unchanged.

Example 8

This example provides a nylon composite having both abrasion resistance and antistatic property, which is the same as example 1 except that the molecular weight of the ultra-high molecular weight polyethylene is 250 ten thousand.

Example 9

This example provides a nylon composite having both abrasion resistance and antistatic property, which is the same as example 1 except that the molecular weight of the ultra-high molecular weight polyethylene is 600 ten thousand.

Example 10

This example provides a nylon composite material having both abrasion resistance and antistatic property, which is the same as example 1 except that the carbon nanotube a is directly obtained from a commercially available carbon nanotube.

Example 11

This example provides a nylon composite having both abrasion resistance and antistatic property, which is the same as example 1 except that the anionic surfactant is replaced with sodium hexadecyl sulfonate.

The speed of the mixer in the above-described embodiments is not adjusted merely for time-saving reasons, and other suitable speeds of rotation are equally possible to achieve the above-described mixing.

Second, comparative example

Comparative example 1

This comparative example provides a nylon composite, which was otherwise the same as example 1, without the addition of carbon nanotubes.

Comparative example 2

This comparative example provides a nylon composite that was otherwise the same as in example 1, except that no ultra-high molecular weight polyethylene was added to the nylon composite.

Comparative example 3

This comparative example provides a nylon composite that is 100% nylon 66 chip, all other things being equal to example 1.

Comparative example 4

The comparative example provides a nylon composite material, except that the proportion of each component is modified into 685g of nylon 66 slices; the same procedure as in example 1 was repeated, except that the amount of the other components was changed to 250g of the ultrahigh-molecular weight polyethylene.

Comparative example 5

The comparative example provides a nylon composite material, except that the proportion of each component is modified to be 905g of nylon 66 slices; the same procedure as in example 1 was repeated except that the amount of the ultrahigh-molecular weight polyethylene was changed to 30g, and the contents of the other components were changed.

Third, test and results

The test method comprises the following steps: the tensile strength is tested by adopting an ASTM D638-2003 method; the bending strength is tested by adopting an ASTMD790-03 method; the impact strength is tested by adopting an ASTMD256-2006 method; the friction coefficient is tested by adopting the GB/T1689-2014 standard; the abrasion is tested by adopting the GB/T1689-2014 standard; the volume resistivity is tested by the GB/T1410-2006 method.

The test results of the above examples and comparative examples are shown in table 1.

TABLE 1

From table 1, the following points can be seen:

(1) the nylon composite material has excellent friction resistance and antistatic performance, the tensile strength is more than 74MPa, the bending strength is more than 101MPa, the impact strength is more than 49MPa, and the volume resistivity is 5.31 multiplied by 10¹¹Omega cm or less, the friction coefficient is less than 0.301, and the abrasion is less than 3.3 mg;

(2) by combining example 1 and comparative examples 1 to 3, it can be seen that in example 1, in which the ultra-high molecular weight polyethylene, the carbon nanotube a and the nylon 66 chip are used together, the friction coefficient of example 1 is 0.201 and the abrasion is only 1.9mg on the basis of the impact strength of 63.2MPa, and the volume resistivity is 2.23 × 10, compared to comparative example 1 in which no carbon nanotube is used, comparative example 2 in which no ultra-high molecular weight polyethylene is used and comparative example 3 in which the nylon is pure nylon⁸Omega cm, whereas the abrasion of comparative example 1 was as high as 3.1mg, the impact strength was only 55.0MPa, and the abrasion of comparative example 2 and comparative example 3 was 4.5mg and 5.8mg, the friction coefficients are 0.441 and 0.490 respectively, and the volume resistivity of the comparative examples 1-3 is higher than that of the example 1, so that the wear resistance is obviously improved and the antistatic performance is improved by adding the carbon nano tube on the basis of ensuring the mechanical performance by combining the three components to form the ternary nano interface film;

(3) it can be seen from the combination of example 1 and comparative examples 4 to 5 that the ratio of the ultra-high molecular weight polyethylene to the nylon in comparative examples 4 to 5 is 0.36:1 and 0.03:1, respectively, and the volume resistivity of comparative examples 4 to 5 is as high as 9.12 × 10⁹Omega cm and 2.12X 10⁹Omega cm, and the impact strengths of comparative example 4 and comparative example 5 are only 58.5MPa and 55.5MPa, respectively, and the abrasion resistance coefficient of comparative example 5 is only 0.397, it can be seen from comparison with example 1 that the present invention can effectively ensure mechanical properties, abrasion resistance, and antistatic properties by controlling the compounding ratio of nylon and ultra-high molecular weight polyethylene in a specific range.

(4) It can be seen from the combination of example 1 and example 10 that the antistatic performance, abrasion resistance and mechanical strength of example 1 are better than those of example 10 when the modified carbon nanotube a is used in example 1 than when the commercially available carbon nanotube is directly used in example 10, thereby showing that the present invention significantly improves the performance of nylon composite material in various aspects by using the modified carbon nanotube.

In conclusion, the nylon composite material provided by the invention has excellent friction resistance and antistatic property, and can be used for manufacturing automobile parts and shuttles in looms; and the preparation method of the nylon composite material is simple, easy to realize industrial operation and wide in application prospect.

The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims

1. The nylon composite material with wear-resisting and antistatic properties is characterized in that the components of the nylon composite material comprise nylon and additive components;

the additive components comprise ultra-high molecular weight polyethylene and carbon nano tubes;

the mass ratio of the ultra-high molecular weight polyethylene to the nylon is 0.05-0.2: 1.

2. The nylon composite material of claim 1, wherein the mass ratio of the carbon nanotubes to the nylon is 0.01-0.03: 1.

3. The nylon composite of claim 1 or 2, wherein the carbon nanotubes are surfactant-modified carbon nanotubes;

preferably, the surfactant comprises an anionic surfactant and/or a cationic surfactant;

preferably, the carbon nanotube is modified by an anionic surfactant and a cationic surfactant in sequence;

preferably, the anionic surfactant has a benzene ring structure;

preferably, the anionic surfactant is negatively charged;

preferably, the anionic surfactant comprises any one or a combination of at least two of N, N-didodecyl-2, 6-pyridinedicarboxamide sodium propionate, N' - (dodecyl di-p-benzenesulfonic acid sodium) ethylenediamine or straight chain alkyl diphenylmethane disulfonate;

preferably, the cationic surfactant comprises any one of tetrabutylammonium chloride, cetyltrimethylammonium chloride or cetyltrimethylammonium bromide or a combination of at least two thereof.

4. The nylon composite of any one of claims 1 to 3, wherein the carbon nanotubes are multi-walled carbon nanotubes;

preferably, the pipe diameter of the carbon nano tube is 10-15 nm;

preferably, the length of the carbon nanotube is 10-30 μm.

5. The nylon composite according to any one of claims 1 to 4, wherein the viscosity average molecular weight of the ultrahigh molecular weight polyethylene is 300 to 400 ten thousand;

preferably, the particle size of the ultra-high molecular weight polyethylene is 120-200 meshes;

preferably, the bulk density of the ultra-high molecular weight polyethylene is 0.4-0.5 g/cm³；

Preferably, the relative viscosity of the nylon is 2.3-3.2.

6. The nylon composite material according to any one of claims 1 to 5, wherein the content of the ultra-high molecular weight polyethylene in the nylon composite material is 5 to 20%;

preferably, the content of the carbon nano tube in the nylon composite material is 1-2%;

preferably, the content of nylon in the nylon composite material is 75-90%.

7. The nylon composite of any one of claims 1-6, further comprising an antioxidant and an interfacial compatibilizer;

preferably, the content of the antioxidant in the nylon composite material is 0.3-1.0%;

preferably, the content of the interfacial compatilizer in the nylon composite material is 0.3-1.0%.

8. The method for preparing a nylon composite material according to any one of claims 1 to 7, wherein the method comprises the following steps: mixing the components of the nylon composite material, and sequentially carrying out melt mixing and extrusion granulation to obtain the nylon composite particles.

9. The method of manufacturing according to claim 8, wherein the mixing is performed in a mixer;

preferably, the temperature of the melt mixing is 220-275 ℃;

preferably, the mixing further comprises modification of the carbon nanotubes;

preferably, the modification of the carbon nanotubes comprises: dispersing the carbon nano tube in a surfactant, and separating to obtain a modified carbon nano tube;

preferably, the modification of the carbon nanotubes comprises: mixing the carbon nano tube and the anionic surfactant, and performing first dispersion and first separation to obtain a first material; mixing the first material and the cationic surfactant, and performing second dispersion and second separation to obtain a modified carbon nanotube;

preferably, the anionic surfactant accounts for 0.1-1% of the mass of the carbon nanotube;

preferably, the cationic surfactant accounts for 0.1-1% of the mass of the carbon nano tube.

10. Use of the nylon composite material with wear resistance and antistatic performance according to any one of claims 1 to 7 in automobile parts or weaving machines.