WO2010127596A1 - 用于机场货运车滚轮的高耐磨尼龙复合材料及其制备方法 - Google Patents

用于机场货运车滚轮的高耐磨尼龙复合材料及其制备方法 Download PDF

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WO2010127596A1
WO2010127596A1 PCT/CN2010/072234 CN2010072234W WO2010127596A1 WO 2010127596 A1 WO2010127596 A1 WO 2010127596A1 CN 2010072234 W CN2010072234 W CN 2010072234W WO 2010127596 A1 WO2010127596 A1 WO 2010127596A1
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Prior art keywords
nylon
wear
composite material
freight car
lubricating
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PCT/CN2010/072234
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English (en)
French (fr)
Inventor
韩政芳
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易达科技(香港)有限公司
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Priority to EP10771999.9A priority Critical patent/EP2436732B1/en
Priority to CA2760229A priority patent/CA2760229C/en
Priority to SG2011079308A priority patent/SG175819A1/en
Priority to US13/266,458 priority patent/US8653178B2/en
Priority to AU2010244900A priority patent/AU2010244900B2/en
Publication of WO2010127596A1 publication Critical patent/WO2010127596A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C08K7/20—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B64—AIRCRAFT; AVIATION; COSMONAUTICS
    • B64F—GROUND OR AIRCRAFT-CARRIER-DECK INSTALLATIONS SPECIALLY ADAPTED FOR USE IN CONNECTION WITH AIRCRAFT; DESIGNING, MANUFACTURING, ASSEMBLING, CLEANING, MAINTAINING OR REPAIRING AIRCRAFT, NOT OTHERWISE PROVIDED FOR; HANDLING, TRANSPORTING, TESTING OR INSPECTING AIRCRAFT COMPONENTS, NOT OTHERWISE PROVIDED FOR
    • B64F1/00—Ground or aircraft-carrier-deck installations
    • B64F1/32—Ground or aircraft-carrier-deck installations for handling freight
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • the present invention relates to a nylon composite material and a method of preparing the same, and more particularly to a high abrasion resistant nylon composite material for use in an airport freight car roller and a method of preparing the same.
  • PA Polyamide
  • Excellent, with impact resistance, is a relatively tough engineering plastic.
  • the characteristics of this material are: 1. High crystallinity, high surface hardness, wear resistance, low friction coefficient, self-lubricating and silencing. 2, low temperature performance is very good, has a certain heat resistance. 3, non-toxic, odorless, no mold, self-extinguishing, good weatherability, but poor dyeability. 4, chemical stability, seawater resistance, solvent resistance, oil resistance, but not acid. 5. Electrical insulation is good, but it is susceptible to temperature. 6, water absorption is large, moisture affects dimensional stability and electrical properties.
  • Nylon 6 PA6
  • nylon 66 PA66
  • Nylon 6 also has good physical and mechanical properties, such as high tensile strength, excellent wear resistance, good impact resistance, and outstanding chemical and oil resistance.
  • Nylon 66 is a homogeneous thermoplastic polymer with 6 symmetrical methylene groups in its molecular structure. It has the advantages of high strength, wear resistance, solvent resistance, self-lubricity and wide temperature range. It is widely used. One of engineering plastics.
  • nylon Due to the excellent properties of nylon, nylon is widely used in industrial manufacturing. For example, in the automotive, instrumentation, machinery, textile and other cities, most of these materials are used as components and structural parts. However, its large water absorption and poor dimensional stability limit its wider range. It can reduce the water absorption rate by filling the reinforcing modifier, ensuring the work under high temperature and high humidity conditions, and at the same time increasing the rigidity and reducing the high temperature creep. Denaturation, shrinkage, improved dimensional stability, impact strength, abrasion resistance and flame retardancy.
  • the general reinforcing modifier is mainly to add glass fiber. The amount of glass fiber added has a great influence on the mechanical properties (impact, tensile and bending strength) of the composite.
  • the lifting platform trucks of the existing airport transportation equipment need to be equipped with rollers, and the rollers can drive the front and rear, left and right and the rotation of the container and the pallet by the roller shaft transmission.
  • the prior art provides an unreasonable design of the roller of aluminum alloy or other metal materials, because the same metal has high mutual solubility and is easy to adhere and cause wear.
  • the wear of the aluminum alloy has two different mechanisms depending on the load. Under low load, slight wear or oxidative wear occurs, and a dense surface oxide film is formed on the surface, and the thickness thereof can be about 2 ⁇ . This layer of oxide film cracks and flakes under the action of friction, producing some fine-grained wear debris.
  • the technical problem to be solved by the present invention is to provide a highly wear-resistant nylon composite material for an airport freight car roller and a preparation method thereof.
  • the technical solution adopted by the present invention to solve the above technical problems is to provide a first high wear-resistant nylon composite material for an airport freight car roller, which is a composite material made of the following weight ratio components: nylon 6 , 60-80%;
  • Lubricating anti-wear agent 5-7 %
  • Antioxidant 0.3-1%
  • the second high-wear nylon composite for airport freight car rollers is a composite made from the following weight ratio components:
  • Nylon 66 60-80%; Glass beads, 5-13%;
  • Lubricating anti-wear agent 5-7 %
  • Antioxidant 0.3-1%
  • a third high wear-resistant nylon composite for airport freight car rollers which is a composite made from the following weight ratio components:
  • Lubricating anti-wear agent 5-7 %
  • Antioxidant 0.3-1%
  • the fourth high-wear nylon composite for airport freight car rollers is a composite made from the following weight ratio components:
  • Glass fiber powder 6-18%
  • Lubricating anti-wear agent 5-7 %.
  • the lubricating wear resist is ultra high molecular weight polyethylene, or is a mixture of polytetrafluoroethylene or ultrahigh molecular weight polyethylene and polytetrafluoroethylene.
  • the surfaces of the glass microspheres and the glass fiber powder are treated with a silicon germanium coupling agent.
  • the component of the fourth high abrasion resistant nylon composite further comprises a graft type toughening modifier in an amount of from 3 to 5% by weight.
  • the graft type toughening modifier is a graft polymerized oligomer of a polyolefin elastomer grafted unsaturated acid or an acid anhydride, and has a melt index of 1.0-5.0 g/10 mm and a graft ratio of 0.5-1%. .
  • the graft polymerized oligomer of the polyolefin elastomer graft unsaturated acid or acid anhydride is a maleic anhydride graft polyolefin elastomer having a melt index of 2 g/10 mm and a graft ratio of 0.8%.
  • composition of the fourth high abrasion resistant nylon composite further includes an antioxidant having a weight ratio of 0.3 to 1%.
  • the antioxidant is a compound system of a hindered phenolic antioxidant and a phosphite antioxidant.
  • the compound system of the hindered phenolic antioxidant and the phosphite antioxidant is an antioxidant 1098/antioxidant 168 in a weight ratio of 1:1.
  • composition of the fourth high abrasion resistant nylon composite further comprises a lubricating dispersant in an amount of from 0.2 to 0.3% by weight.
  • the lubricating dispersant is a stearate.
  • the stearate is selected from one or more of calcium stearate, zinc stearate, and aluminum stearate.
  • the component of the fourth high wear-resistant nylon composite further includes a nucleating agent, and the nucleating agent is contained in a weight ratio of 0.2-0.5.
  • the nucleating agent is a commercially available nucleating agent P-20.
  • the preferred weight ratios of the above-mentioned fourth components of the high abrasion resistant nylon composite for the roller of the airport freight car are:
  • Lubricating anti-wear agent 5-6 %.
  • the first method for preparing a high wear-resistant nylon composite material for an airport freight car roller is as follows: First, the raw material is first weighed according to the following weight percentage, nylon 6, 60-80%; glass beads, 5-13%; glass fiber powder, 6-14%; lubricating wear inhibitor, 5-7 %; graft type toughening modifier accounted for 3-5 %; antioxidants accounted for 0.3-1%; lubricating dispersant accounted for 0.2-0.3%; nucleating agent accounted for 0.2-0.5%; ⁇ second, the above materials were mixed in a high-mixer, and then discharged, and then The pellet was extruded by an extruder at a processing temperature of 210 ° C to 290 ° C.
  • the second method for preparing the high wear-resistant nylon composite material for the roller of the airport freight car is as follows: First, the raw material is first weighed according to the following weight percentage, nylon 66, 60-80%; glass beads, 5-13%; glass fiber powder, 6-14%; lubricating wear-resistant agent, 5-7%; graft type toughening modifier accounted for 3-5%; antioxidant accounted for 0.3-1%; lubricating dispersant 0.2-0.3%; nucleating agent accounts for 0.2-0.5%; In the second step, the above raw materials are mixed in a high-mixer, and then discharged, and then extruded and granulated by an extruder. The processing temperature is 210°. C-290 ° C.
  • the third method for preparing the high wear-resistant nylon composite material for the roller of the airport freight car is as follows: first, the raw materials are first weighed according to the following weight percentage, nylon 6, 18-41%; nylon 66, 28 -42%; glass beads, 5-13%; glass fiber powder, 6-14%; lubricating wear inhibitor, 5-7%; graft type toughening modifier accounted for 3-5%; antioxidants accounted for 0.3-1%; lubricating dispersant accounts for 0.2-0.3%; nucleating agent accounts for 0.2-0.5%; ⁇ Second, the above raw materials are mixed in a high-mixer, and then discharged, and then extruded by an extruder. Granulation, processing temperature is 210 ° C -290 ° C.
  • the fourth method for preparing a high wear-resistant nylon composite material for an airport freight car roller is as follows: First, the raw material is first weighed according to the following weight percentage, nylon 6 or nylon 66 or nylon 6 and nylon 66 Mixture, 60-80%; glass beads, 5-16%; glass fiber powder, 6-18%; lubricating wear-resistant agent, 5-7%; ⁇ 2, the above materials are mixed in a high-mixer Then, the material is discharged, and then extruded and granulated by an extruder, and the processing temperature is 210 ° C - 290 ° C.
  • the method for preparing a highly wear-resistant nylon composite material for an airport freight car roller may also adopt another process as follows: First, the raw material, nylon 6 or nylon 66 or nylon is first weighed according to the following weight percentages. Mixture of 6 and nylon 66 accounted for 60-80%; glass beads accounted for 5-13%; glass fiber powder accounted for 6-14%; lubricating wear agent accounted for 5-7%; graft type toughening modifier accounted for 3 -5%; antioxidants accounted for 0.3-1%; lubricating dispersant accounted for 0.2-0.3%; nucleating agent accounted for 0.2-0.5%; ⁇ second, the above materials were mixed in a high-mixer, and then discharged Then, it is extruded and granulated by an extruder, and the processing temperature is 210 ° C -290 ° C.
  • the high wear-resistant nylon 6, nylon 66 and nylon 6/nylon 66 composite materials of the invention have high friction coefficient, are not easy to wear, have good toughness, strong hardness, and can withstand large impact forces. Ideal for manufacturing rollers on transport vehicles.
  • the roller made of the above high wear-resistant material has good toughness and strong hardness, and can withstand large impact force.
  • the frosted texture surface can provide additional anti-slip property.
  • Figure 1 is a perspective view of a roller on an elevator car platform of an airport freight transporter constructed using the high wear resistant nylon composite of the present invention.
  • the invention relates to a high wear resistant nylon 6 composite material and a preparation method thereof.
  • the high wear-resistant nylon 6 (PA6) composite material is mainly composed of nylon 6 (PA6), glass microbeads (GB), glass fiber powder (GF) and lubricating wear-resistant agent, and the rest are auxiliary materials.
  • the high wear resistant nylon 6 composite consists of the following components and weight percentages of raw materials:
  • the viscosity of the nylon 6 is 2.4; the glass microbeads and the glass fiber powder are alkali-free glass microspheres and alkali-free glass fiber powder, the surface of which is treated by a silicon germanium coupling agent; the ultrahigh molecular weight polyethylene is the first Lubricating anti-wear agent; the polytetrafluoroethylene is a second lubricating anti-wear agent; the graft-type toughening modifier is a graft polymerized oligomer of a polyolefin elastomer (POE) graft unsaturated acid or anhydride
  • POE polyolefin elastomer
  • the graft type toughening modifier is a maleic anhydride grafted polyolefin elastomer (POE), which is melted.
  • the index is 2g/10mm, and the graft ratio is 0.8%;
  • the oxygen agent is a compound system of a hindered phenolic antioxidant and a phosphite antioxidant, for example, the antioxidant is 1098/168 (weight ratio is 1:1), and 1098 is N, N'-1.
  • 6-hexylene-di-[3,5-di-tert-butyl-4-hydroxyphenylpropanamide], 168 is (2,4 di-tert-butylphenyl)phosphite triester;
  • the lubricating dispersant is stearic acid
  • Calcium acid may also be one or more of stearates such as zinc stearate and aluminum stearate;
  • the nucleating agent is a calcium carboxylate salt having a long carbon chain as a main component, for example, commercially available.
  • Nuclear agent P-20 which can be produced by Clariant, Germany.
  • the above components were placed in a high-mixer for 5-10 minutes, discharged, and then extruded and granulated by a screw extruder at a processing temperature of 210-255 ° C and a screw rotation number of 400-600 rpm.
  • the invention also provides a preparation method of a high wear-resistant nylon 6 (PA6) composite material, and the preparation process thereof is as follows: Step 1: The raw material is weighed according to the following weight percentage, the nylon 6 is 69%, and the surface is silicon germanium. Coupling agent treated glass beads 10%, glass fiber powder treated with silicon germanium coupling agent 10%, first lubricating wear agent (ultra high molecular weight polyethylene) 3%, second lubricating wear agent (poly Tetrafluoroethylene) 3%, graft type toughening modifier 4%, according to the weight ratio of 1:1 compounded antioxidant 1098/168 compound system 0.5%, lubricating dispersant calcium stearate 0.2%, Nucleating agent 0.3%; Step 2: The above original The material was placed in a high-mixer for 5 minutes, and then discharged, and then extruded and granulated by a twin-screw extruder at a processing temperature of 215-245 ° C and a screw rotation number of 600 rpm.
  • the graft type toughening modifier is a graft polymerized oligomer of a polyolefin elastomer (POE) grafted unsaturated acid or an acid anhydride. Further, the graft type toughening modifier is maleic anhydride.
  • POE polyolefin elastomer
  • the grafted polyolefin elastomer (POE) has a melt index of 2 g/10 min and a graft ratio of 0.5 to 1%.
  • the invention also provides a preparation method of another high wear-resistant PA6 composite material, and the preparation process thereof is as follows: Step 1: The raw material weighed by weight percentage, nylon 6 accounts for 70%, and the surface is coated with silicon germanium coupling agent The treated glass beads accounted for 10%, the surface treated with silicon germanium coupling agent accounted for 10% of the glass fiber powder, the graft type toughening modifier 3%, and the first lubricating wear agent (ultra high molecular weight polyethylene) accounted for 3%, the second lubricant wear-resistant agent (polytetrafluoroethylene) accounted for 3%, according to the weight ratio of 1:1 compounded antioxidant 1098/168 compound system accounted for 0.3%, lubricating dispersant calcium stearate accounted for 0.2%, nucleating agent accounted for 0.5%; Step 2: The above materials were mixed in a high-mixer for 3 minutes, discharged according to the post, and then extruded and granulated by a twin-screw extruder. The processing
  • the invention also provides a preparation method of another high wear-resistant PA6 composite material, and the preparation process thereof is as follows: Step 1: The raw material weighed by weight percentage, nylon 6 accounts for 67.2%, and the surface is coated with silicon germanium coupling agent The treated glass beads accounted for 10%, the surface treated with silicon germanium coupling agent accounted for 10% of the glass fiber powder, the first lubricating wear agent (ultra high molecular weight polyethylene) accounted for 3%, and the second lubricating wear agent (polymerized) Tetrafluoroethylene) 3%, graft type toughening modifier 5%, according to the weight ratio of 1:1 compounded antioxidant 1098/168 compound system accounted for 1%, lubricating dispersant calcium stearate accounted for 0.3%, nucleating agent accounted for 0.5%; Step 2: The above materials were mixed in a high-mixer for 3 minutes, discharged according to the post, and then extruded and granulated by a twin-screw extruder. The processing temperature
  • the invention also relates to a highly abrasion resistant nylon 66 composite and a process for the preparation thereof.
  • the high wear-resistant nylon 66 (PA66) composite material is mainly composed of nylon 66 (PA66), glass microbeads (GB), glass fiber powder (GF) and lubricating wear-resistant agent, and the rest are auxiliary materials.
  • the high wear resistance The nylon 66 composite consists of the following components and weight percentages of raw materials:
  • the viscosity of the nylon 66 is 2.4; the glass microbeads and the glass fiber powder are alkali-free glass microspheres and alkali-free glass fiber powder, the surface of which is treated by a silicon germanium coupling agent; the ultrahigh molecular weight polyethylene is the first lubrication An anti-wear agent, the polytetrafluoroethylene is a second lubricating anti-wear agent; the graft-type toughening modifier is a graft polymerized oligomer of a polyolefin elastomer (POE) grafted unsaturated acid or an acid anhydride, Its melt index is 1.0-5.0 g/10 mm, the graft ratio is 0.5-1%.
  • POE polyolefin elastomer
  • the antioxidant is a compound system of a hindered phenolic antioxidant and a phosphite antioxidant.
  • the antioxidant is 1098/168 (weight ratio is 1:1), and 1098 is N, N'. -1,6-hexylene-di-[3,5-di-tert-butyl-4-hydroxybenzenepropanamide], 168 is a (2,4-di-tert-butylphenyl)phosphite triester.
  • the lubricating dispersing agent is calcium stearate, and may be one or more of stearic acid such as zinc stearate or aluminum stearate.
  • the nucleating agent is a calcium carboxylate salt containing a long carbon chain as a main component, such as a commercially available nucleating agent P-20, which can be produced by Clariant, Germany.
  • the above components were placed in a high-mixer in a ratio of 5 to 10 minutes, discharged, and then extruded and granulated by a screw extruder at a processing temperature of 245 to 290 ° C and a screw rotation number of 400 to 600 rpm.
  • a preparation method of a highly wear-resistant PA66 composite material is prepared as follows: In the first step, the raw material weighed by weight percentage, PA66 accounts for 69%, and the glass microbead treated with the silicon germanium coupling agent accounts for 10%. Glass fiber powder treated with silicon germanium coupling agent accounted for 10%, first lubricant wear agent (ultra high molecular weight polyethylene) accounted for 3%, and second lubricant wear agent (polytetrafluoroethylene) accounted for 3%. The branch toughening modifier accounted for 4%, the antioxidant 1098/168 compound system accounted for 0.5% by weight of 1:1, the lubricating dispersant calcium stearate accounted for 0.2%, and the nucleating agent accounted for 0.3%.
  • Step 2 put the above mixture into the high The mixture was mixed for 5 minutes, then discharged, and then extruded and granulated by a twin-screw extruder at a processing temperature of 250-265 ° C and a screw rotation number of 600 rpm.
  • the graft type toughening modifier is a graft polymerized oligomer of a polyolefin elastomer (POE) graft unsaturated acid or an acid anhydride, which is a maleic anhydride grafted polyolefin elastomer (POE), and its melt index
  • POE polyolefin elastomer
  • the graft ratio was 0.5-1% at 2 g/10 min.
  • the preparation method of the high wear-resistant PA66 composite material is as follows: First, the raw materials weighed by weight percentage: PA66 accounts for 73%, and the glass microbeads treated with the silicon germanium coupling agent account for 10%. The glass fiber powder treated with silicon germanium coupling agent accounts for 10%, the first lubricating wear agent (ultra high molecular weight polyethylene) accounts for 3%, and the second lubricating wear agent (polytetrafluoroethylene) accounts for 3%.
  • a preparation method of a highly wear-resistant PA66 composite material is prepared as follows: In the first step, the raw material weighed by weight percentage, PA66 accounts for 68.5%, and the glass microbead treated with the silicon germanium coupling agent accounts for 10%. Glass fiber powder treated with silicon germanium coupling agent accounted for 10%, first lubricant wear agent (ultra high molecular weight polyethylene) accounted for 3%, and second lubricant wear agent (polytetrafluoroethylene) accounted for 3%.
  • the branch type toughening modifier accounted for 4%, the antioxidant 1098/168 compound system accounted for 1% by weight, the compounding system accounted for 1%, the lubricating dispersing agent calcium stearate accounted for 0.2%, and the nucleating agent accounted for 0.3%.
  • the above mixture is mixed in a high-mixer for 5 minutes, and then discharged, and then extruded and granulated by a twin-screw extruder.
  • the processing temperature is 250-265 ° C, and the screw rotation speed is 600 rpm. .
  • the present invention further relates to a highly abrasion resistant nylon 6/nylon 66 composite and a process for its preparation.
  • the high wear-resistant nylon 6/nylon 66 composite material is mainly composed of nylon 6, nylon 66, glass microbeads, glass fiber powder and lubricating wear-resistant agent, and the rest are auxiliary materials.
  • the high abrasion resistant nylon 6/nylon 66 composite consists of the following components and weight percent of raw materials:
  • the nylon 6 and nylon 66 had a viscosity of 2.4, and the nylon 66 had a viscosity of 2.8.
  • the glass fiber powder is an alkali-free glass microsphere and an alkali-free glass fiber powder, and the surface thereof is treated by a silicon germanium coupling agent;
  • the ultrahigh molecular weight polyethylene is a first lubricating wear resisting agent, and the polytetrafluoroethylene is a second lubricating resistant Grinding agent;
  • the graft type toughening modifier is a graft polymerized oligomer of a polyolefin elastomer (POE) grafted unsaturated acid or anhydride, and has a melt index of 1.0-5.0 g/10 min, a graft ratio It is 0.5-1%.
  • the antioxidant is a compound system of a hindered phenolic antioxidant and a phosphite antioxidant.
  • the antioxidant is 1098/168 (weight ratio is 1:1), and 1098 is N, N'- 1,6-Hexylene-di-[3,5-di-tert-butyl-4-hydroxybenzenepropanamide], 168 is a (2,4 di-tert-butylphenyl)phosphite triester.
  • the lubricating dispersing agent is calcium stearate, and may be one or more of stearic acid salts such as zinc stearate and aluminum stearate.
  • the nucleating agent is a calcium carboxylate salt containing a long carbon chain as a main component, such as a commercially available nucleating agent P-20, which can be produced by Clariant, Germany.
  • the above components were placed in a high-mixer for 5-10 minutes, discharged, and then extruded and granulated by a screw extruder at a processing temperature of 235-280 ° C and a screw rotation number of 400-600 rpm.
  • the screw combination is a specific combination with good dispersion.
  • a preparation method of high wear-resistant PA6/PA66 composite material is as follows: Raw materials weighed: PA6 is 39%, PA66 is 30%, glass beads treated with silicon germanium coupling agent 10%, glass fiber powder treated with silicon germanium coupling agent 10%, first lubrication Anti-wear agent (ultra-high molecular weight polyethylene) 3%, second lubricant wear-resistant agent (polytetrafluoroethylene) 3%, graft type toughening modifier 4%, according to the weight ratio of 1: 1 compound Oxygen agent 1098/168 compound system 0.5%, lubricating dispersing agent calcium stearate 0.2%, nucleating agent 0.3%. It was mixed in a high-mixer for 5 minutes, discharged, and then extruded and granulated by a twin-screw extruder at a processing temperature of 245-265 ° C and a screw rotation number of 600 rpm.
  • the graft type toughening modifier is a graft polymerized oligomer of a polyolefin elastomer (POE) graft unsaturated acid or an acid anhydride, which is a maleic anhydride grafted polyolefin elastomer (POE), and its melt index
  • POE polyolefin elastomer
  • the graft ratio was 0.5-1% at 2 g/10 min.
  • a preparation method of a highly wear-resistant PA6/PA66 composite material which is prepared as follows: raw materials weighed by weight: PA6, 33%; PA66, 40%; glass beads treated with a silicon germanium coupling agent, 10%; glass fiber powder treated with silicon germanium coupling agent, 10%; first lubricating wear agent (ultra high molecular weight polyethylene), 3%; second lubricating wear agent (polytetrafluoroethylene), 3 %; an antioxidant 1098/168 compound system with a weight ratio of 1:1, 0.3%; a lubricating dispersing agent calcium stearate, 0.2%; a nucleating agent, 0.5%. It was mixed in a high-mixer for 3 minutes, discharged, and then granulated by a twin-screw extruder at a processing temperature of 245-275 ° C and a screw rotation number of 550 rpm.
  • a preparation method of a highly wear-resistant PA6/PA66 composite material which is prepared as follows: raw materials weighed by weight: PA6 is 38.3%, PA66 is 30%, and glass beads 10 surface treated with silicon germanium coupling agent %, glass fiber powder treated with silicon germanium coupling agent 10%, first lubricating wear agent (ultra high molecular weight polyethylene) 3%, second lubricating wear agent (polytetrafluoroethylene) 3%, grafted Type toughening modifier 4%, according to the weight ratio of 1:1 compounded antioxidant 1098/168 compound system 1%, lubricating dispersing agent calcium stearate 0.2%, nucleating agent 0.5%. It was mixed in a high-mixer for 5 minutes, discharged, and then extruded and granulated by a twin-screw extruder at a processing temperature of 245-265 ° C and a screw rotation number of 600 rpm.
  • PA6/PA66 composite material composed of the following components and weight percentages Table 10: Proportion 28-33
  • the above components were placed in a high-mixer for 5-10 minutes, discharged, and then extruded and granulated by a screw extruder at a processing temperature of 235-280 ° C and a screw rotation number of 400-600 rpm.
  • the screw combination is a specific combination with good dispersion.
  • a highly wear resistant PA6/PA66 composite consisting of the following components and weight percent (wt%) of raw materials:
  • Nucleating agent (P-20) 0 0 0 0 0 0 0.2 0.5
  • the above components are placed in a high-mixer for 5-10 minutes, discharged, and then extruded and granulated by a screw extruder. Processing temperature At 235-280 ° C, the number of screw revolutions is between 400 and 600 rpm.
  • the screw combination is a specific combination with good dispersion.
  • the invention also provides a roller made of high wear-resistant nylon 6 (PA6), nylon 66 (PA66), nylon 6 ( ⁇ 6) / nylon 66 ( ⁇ 66) composite material, which is used for lifting and lowering of airport cargo transit vehicles.
  • Platform type device As shown in FIG. 1, the roller 110 has a shaft traversing a shaft hole 111.
  • the roller rotating shaft can be installed in the shaft hole 111, and the roller shaft frame is fixed by the roller rotating shaft for transportation.
  • the front and rear ends 112 of the roller 110 are provided with a planar structure to cooperate with other tracks.
  • the outer surface 113 of the roller 110 is a matte texture that increases the friction between the roller and the bottom plate of the container and the bottom of the pallet when transporting the object.
  • the nylon roller 110 is made of nylon, which is durable, not easy to wear, and does not slip.
  • the nylon material of the invention has a very reasonable material design, especially when transporting objects in any environment and weather, and the friction between the roller and the container bottom plate and the bottom plate of the container plate is increased, which is not easy to slip, and the friction during transmission is not easy to generate noise. It is not easy to wear, has low noise, and is environmentally friendly.
  • the roller is durable, tough, strong and strong, and can withstand large impact forces.
  • the matte texture can provide additional anti-slip properties. Avoid the peeling of powder when metal and metal rotate, pollute the environment, and prevent metal powder from entering the eyes and respiratory tract to cause harm to the human body.
  • the high wear-resistant nylon 6 PA6;>, nylon 66 PA66;>, nylon 6 (PA6)/nylon 66 (PA66) composite material of the invention can also be made into other products, which can be widely used in automobiles, Mechanical equipment connectors, gears, oilfield equipment, instrumentation, textile equipment, electrical and electronic equipment, and household appliances.

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Description

用于机场货运车滚轮的高耐磨尼龙复合材料及其制备方法
技术领域 本发明涉及尼龙复合材料及其制备方法，尤其是指用于机场货运车滚轮的 高耐磨尼龙复合材料及其制备方法。
说 背景技术 聚酰胺 （PA) 俗称尼龙， 其酰胺基团有极性， 能形成氢健， 所以机械性 书
能优秀， 具有杭冲击性， 是相对坚韧的工程塑料。 这种材料的特点是： 1、 结 晶度高， 表面硬度大， 耐磨损， 摩擦系数小， 有自润滑性和消音性。 2、 低温 性能很好， 有一定的耐热性。 3、 无毒、 无臭、 无霉烂， 有自熄性， 耐候性好， 但染色性差。 4、 化学稳定好， 耐海水、 耐溶剂、 耐油， 但不耐酸。 5、 电绝缘 性好， 但易受温度的影响。 6、 吸水性大， 水分影响尺寸稳定性和电性能。
尼龙 6 (PA6)和尼龙 66 (PA66) 是尼龙的主要品种。 尼龙 6也具有良好 的物理、 机械性能， 例如拉伸强度高， 耐磨性优异， 抗冲击性能好， 耐化学品 和耐油性突出。 尼龙 66是一种分子结构内含 6个对称亚甲基的均匀热塑性高 分子聚合物， 具有强度高、 耐磨、 耐溶剂、 自润滑性好和使用温度范围广等优 点， 是用途比较广泛的工程塑料之一。
由于尼龙具有优异的性能，所以尼龙在工业制造中应用很广泛，如在汽车、 仪器仪表、 机械、 纺织等领城中， 大多采用这种材料作为零部件和结构件。但 其吸水大， 尺寸稳定性差等不足又限制了其更大范围的作用， 可以通过填充增 强改性剂来减少吸水率， 保证在高温高湿条件下工作， 同时更可以增加刚性， 降低高温蠕变性、 收缩率， 提高尺寸稳定性、 冲击强度、 耐磨性和阻燃性。一 般的增强改性剂主要是添加玻璃纤维，玻璃纤维添加量的大小对复合材料的力 学性能 （冲击、 拉伸、 弯曲强度大） 影响较大。 众所周知，现有机场运输设备的升降平台车都需要装设滚轮，滚轮通过滚 轮轴传动可推动集装箱、集装板前后、左右和旋转。现有技术提供铝合金或其 他金属材质的滚轮设计不合理， 因相同金属互溶性大， 易于粘着而导致磨损。 且铝合金的磨损随载荷不同也有两个不同的机制，在低载荷下发生的是轻微磨 损或称氧化磨损， 在表面形成一层致密的表面氧化膜， 其厚度可达 2μπι左右。 在摩擦力作用下这层氧化膜破裂和剥落，产生一些细片状的磨损碎屑。尤其是 在下雨天时容易发生打滑，输送所需物体失控， 需要用人手将物体推动和转换 正确方向， 每年会发生很多因推动物体引致工人滑倒受伤的事故。此外， 现有 的铝合金滚轮容易磨损集装箱底板和集装板底板， 而且摩擦时产生噪音太大， 引致对人体耳朵的损害。 发明内容 本发明要解决的技术问题在于提供用于机场货运车滚轮的高耐磨尼龙复 合材料及其制备方法。
本发明解决上述技术问题所采用的技术方案是:提供第一种用于机场货运 车滚轮的高耐磨尼龙复合材料， 它是由下述重量配比的组分制成的复合材料： 尼龙 6， 60-80%；
玻璃微珠， 5-13%;
玻璃纤维粉， 6-14%;
润滑耐磨剂， 5-7 % ;
接枝型增韧改性剂， 3-5%;
抗氧剂， 0.3-1%;
润滑分散剂， 0.2-0.3%;
成核剂， 0.2-0.5%。
第二种用于机场货运车滚轮的高耐磨尼龙复合材料，它是由下述重量配比 的组分制成的复合材料：
尼龙 66， 60-80%； 玻璃微珠， 5-13%;
玻璃纤维粉， 6-14%;
润滑耐磨剂， 5-7 % ;
接枝型增韧改性剂， 3-5%;
抗氧剂， 0.3-1%;
润滑分散剂， 0.2-0.3%;
成核剂， 0.2-0.5%。
第三种用于机场货运车滚轮的高耐磨尼龙复合材料，它是由下述重量配比 的组分制成的复合材料：
尼龙 6， 18-41%；
尼龙 66， 28-42%；
玻璃微珠， 5-13%;
玻璃纤维粉， 6-14%;
润滑耐磨剂， 5-7 % ;
接枝型增韧改性剂， 3-5%;
抗氧剂， 0.3-1%;
润滑分散剂， 0.2-0.3%;
成核剂， 0.2-0.5%。
第四种用于机场货运车滚轮的高耐磨尼龙复合材料，它是由下述重量配比 的组分制成的复合材料：
尼龙 6或者尼龙 66或者尼龙 6与尼龙 66的混合物， 60-80%;
玻璃微珠， 5-16%;
玻璃纤维粉， 6-18%;
润滑耐磨剂， 5-7 %。
所述润滑耐磨剂为超高分子量聚乙烯，或者为聚四氟乙烯，或者超高分子 量聚乙烯与聚四氟乙烯的混合物。
所述玻璃微珠和玻璃纤维粉的表面经过硅垸偶联剂处理。 所述第四种高耐磨尼龙复合材料的组分还包括接枝型增韧改性剂，该接枝 型增韧改性剂的含量为重量比为 3-5 %。
所述接枝型增韧改性剂为聚烯烃弹性体接枝不饱和酸或者酸酐的接枝聚 合的低聚物， 其熔融指数为 1.0-5.0g/10mm， 接枝率为 0.5-1 %。
所述聚烯烃弹性体接枝不饱和酸或者酸酐的接枝聚合的低聚物为马来酸 酐接枝聚烯烃弹性体， 其熔融指数为 2g/10mm， 接枝率为 0.8 %。
所述第四种高耐磨尼龙复合材料的组分还包括抗氧剂，该抗氧剂含量为重 量比 0.3-1 %。
所述抗氧剂为一种受阻酚类抗氧剂与亚磷酸酯类抗氧剂的复配体系。 所述受阻酚类抗氧剂与亚磷酸酯类抗氧剂的复配体系为重量比为 1 : 1的 抗氧剂 1098/抗氧剂 168。
所述第四种高耐磨尼龙复合材料的组分还包括润滑分散剂，该润滑分散剂 的含量为重量比 0.2-0.3 %。
所述润滑分散剂为硬脂酸盐。
所述硬脂酸盐选自硬脂酸钙， 硬脂酸锌， 硬脂酸铝中的一种或者几种。 所述第四种高耐磨尼龙复合材料的组分还包括成核剂，该成核剂的含量为 重量比 0.2-0.5
所述成核剂为市售成核剂 P-20。
上述第四种用于机场货运车滚轮的高耐磨尼龙复合材料各组分的优选重 量配比为：
尼龙 6或者尼龙 66或者尼龙 6与尼龙 66的混合物， 69-73%;
玻璃微珠， 5-12%;
玻璃纤维粉， 10-17%;
润滑耐磨剂， 5-6 %。
上述第一种用于机场货运车滚轮的高耐磨尼龙复合材料的制备方法，其工 艺为： 歩骤一， 先按以下重量百分比称取原料， 尼龙 6， 60-80%； 玻璃微珠， 5-13%； 玻璃纤维粉， 6-14%; 润滑耐磨剂， 5-7 % ; 接枝型增韧改性剂占 3-5 %; 抗氧剂占 0.3-1%; 润滑分散剂占 0.2-0.3%; 成核剂占 0.2-0.5%; 歩骤二， 将以上原料放入高混机中混合均匀， 然后出料， 再用挤出机挤出造粒， 加工温 度为 210°C-290°C。
上述第二种用于机场货运车滚轮的高耐磨尼龙复合材料的制备方法，其工 艺为： 歩骤一， 先按以下重量百分比称取原料， 尼龙 66， 60-80%； 玻璃微珠， 5-13%； 玻璃纤维粉， 6-14%; 润滑耐磨剂， 5-7%; 接枝型增韧改性剂占 3-5 %; 抗氧剂占 0.3-1%; 润滑分散剂占 0.2-0.3%; 成核剂占 0.2-0.5%; 歩骤二， 将以上原料放入高混机中混合均匀， 然后出料， 再用挤出机挤出造粒， 加工温 度为 210°C-290°C。
上述第三种用于机场货运车滚轮的高耐磨尼龙复合材料的制备方法，其工 艺为：歩骤一，先按以下重量百分比称取原料，尼龙 6， 18-41%;尼龙 66,28-42%; 玻璃微珠， 5-13%; 玻璃纤维粉， 6-14%; 润滑耐磨剂， 5-7%; 接枝型增韧改 性剂占 3-5%; 抗氧剂占 0.3-1%; 润滑分散剂占 0.2-0.3%; 成核剂占 0.2-0.5 %； 歩骤二， 将以上原料放入高混机中混合均匀， 然后出料， 再用挤出机挤出 造粒， 加工温度为 210°C-290°C。
上述第四种用于机场货运车滚轮的高耐磨尼龙复合材料的制备方法，其工 艺为： 歩骤一， 先按以下重量百分比称取原料， 尼龙 6或者尼龙 66或者尼龙 6和尼龙 66的混合物， 60-80%; 玻璃微珠， 5-16%; 玻璃纤维粉， 6-18%; 润 滑耐磨剂， 5-7%; 歩骤二， 将以上原料放入高混机中混合均匀， 然后出料， 再用挤出机挤出造粒， 加工温度为 210°C-290°C。
在本发明中，制备用于机场货运车滚轮的高耐磨尼龙复合材料的方法还可 采用如下另一种工艺： 歩骤一， 先按以下重量百分比称取原料， 尼龙 6或者尼 龙 66或者尼龙 6和尼龙 66的混合物占 60-80%; 玻璃微珠占 5-13%; 玻璃纤 维粉占 6-14%; 润滑耐磨剂占 5-7%; 接枝型增韧改性剂占 3-5%; 抗氧剂占 0.3-1%； 润滑分散剂占 0.2-0.3%; 成核剂占 0.2-0.5%; 歩骤二， 将以上原料 放入高混机中混合均匀， 然后出料， 再用挤出机挤出造粒， 加工温度为 210°C -290 °C。 相对于现有技术， 本发明高耐磨的尼龙 6、 尼龙 66以及尼龙 6/尼龙 66复 合材料具有摩擦系数高， 不易磨损， 韧性好、 坚硬度特强， 能承受较大冲击力 等优点， 非常适合用于制造运输车上的滚轮。利用以上高耐磨材料制成的滚轮 韧性好、 坚硬度特强， 能承受较大冲击力， 除了该材质已有防滑作用外， 磨沙 质感外表更能额外提供防滑性。 附图说明
图 1 是利用本发明高耐磨尼龙复合材料制造的机场货物运输车升降平台 装置上的滚轮的立体图。
具体实施方式 下面根据具体实施方式对本发明作进一歩阐述。
本发明涉及到一种高耐磨尼龙 6复合材料及其制备方法。
实施例 1-6
该高耐磨尼龙 6 (PA6) 复合材料以尼龙 6 (PA6)、 玻璃微珠 （GB) 、 玻 璃纤维粉 （GF) 以及润滑耐磨剂为主要材料， 其余为辅助材料。 该高耐磨尼 龙 6复合材料由以下组分和重量百分比的原料组成：
表 1 : 配比 1-6
Figure imgf000009_0001
其中， 该尼龙 6的粘度为 2.4; 该玻璃微珠和玻璃纤维粉为无碱玻璃微珠 和无碱玻璃纤维粉， 其表面经硅垸偶联剂处理； 该超高分子量聚乙烯为第一润 滑耐磨剂； 该聚四氟乙烯为第二润滑耐磨剂； 该接枝型增韧改性剂为聚烯烃弹 性体 （POE) 接枝不饱和酸或者酸酐的接枝聚合的低聚物， 其熔融指数为 1.0-5.0g/10min, 接枝率为 0.5-1 %， 进一歩地， 该接枝型增韧改性剂为马来酸 酐接枝聚烯烃弹性体（POE), 其熔融指数为 2g/10mm， 接枝率为 0.8% ; 该抗 氧剂为一种受阻酚类抗氧剂与亚磷酸酯类抗氧剂的复配体系，例如该抗氧化剂 为 1098/168 (重量比为 1 :1 )， 1098为 N,N'-1,6-亚己基 -二- [3,5-二叔丁基 -4- 羟基苯丙酰胺]， 168为 （2， 4 二叔丁基苯基） 亚磷酸三酯； 该润滑分散剂为 硬脂酸钙， 还可为硬脂酸锌， 硬脂酸铝等硬脂酸盐中的一种或者几种； 该成核 剂是以长碳链为主要成分的羧酸钙盐， 例如市售成核剂 P-20, 该 P-20可以是 德国科莱恩公司生产的。
将上述组分按比例放入高混机中混合 5-10分钟， 出料， 然后用螺杆挤出 机挤出造粒， 加工温度在 210-255°C， 螺杆转数在 400-600rpm。
表 2: 各段加热温度
Figure imgf000010_0001
根据实施例 1-6制得的样品 1-6， 进行力学性能测试对比， 采用 ASTM标
I试性能对比
Figure imgf000010_0002
实施例 7
本发明还提供了一种高耐磨尼龙 6 (PA6) 复合材料的制备方法， 其制备 工艺歩骤如下： 歩骤一： 按以下重量百分比称取原料， 尼龙 6为 69%， 表面经 硅垸偶联剂处理的玻璃微珠 10%， 表面经硅垸偶联剂处理的玻璃纤维粉 10%, 第一润滑耐磨剂 （超高分子量聚乙烯） 3%， 第二润滑耐磨剂 （聚四氟乙烯） 3%， 接枝型增韧改性剂 4 %， 按照重量比为 1 : 1复配的抗氧剂 1098/168 复 配体系 0.5 %， 润滑分散剂硬脂酸钙 0.2 %， 成核剂 0.3 % ; 歩骤二： 将以上原 料放入高混机中混合 5分钟， 然后出料， 再用双螺杆挤出机挤出造粒， 加工温 度在 215-245°C， 螺杆转数为 600rpm。
该接枝型增韧改性剂为聚烯烃弹性体（POE)接枝不饱和酸或者酸酐的接 枝聚合的低聚物， 进一歩地， 该接枝型增韧改性剂为马来酸酐接枝聚烯烃弹性 体 （POE) , 其熔融指数为 2g/10min， 接枝率为 0.5-1 %。
实施例 8
本发明还提供了另一种高耐磨 PA6复合材料的制备方法， 其制备工艺歩 骤如下： 歩骤一： 按重量百分比称取的原料， 尼龙 6占 70%， 表面经硅垸偶联 剂处理的玻璃微珠占 10%， 表面经硅垸偶联剂处理的玻璃纤维粉占 10%， 接 枝型增韧改性剂 3 %， 第一润滑耐磨剂 （超高分子量聚乙烯） 占 3%， 第二润 滑耐磨剂（聚四氟乙烯）占 3%，按照重量比为 1 : 1复配的抗氧剂 1098/168 复 配体系占 0.3 %， 润滑分散剂硬脂酸钙占 0.2 %， 成核剂占 0.5 % ; 歩骤二： 将 以上原料放入高混机中混合 3分钟， 按后出料， 再用双螺杆挤出机挤出造粒， 加工温度在 210-235°C， 螺杆转数为 550rpm。
实施例 9
本发明还提供了另一种高耐磨 PA6复合材料的制备方法， 其制备工艺歩 骤如下： 歩骤一： 按重量百分比称取的原料， 尼龙 6占 67.2%， 表面经硅垸偶 联剂处理的玻璃微珠占 10%， 表面经硅垸偶联剂处理的玻璃纤维粉占 10%， 第一润滑耐磨剂（超高分子量聚乙烯） 占 3%， 第二润滑耐磨剂（聚四氟乙烯） 占 3%，接枝型增韧改性剂 5 %，按照重量比为 1 : 1复配的抗氧剂 1098/168 复 配体系占 1 %， 润滑分散剂硬脂酸钙占 0.3 %， 成核剂占 0.5 % ; 歩骤二： 将以 上原料放入高混机中混合 3分钟， 按后出料， 再用双螺杆挤出机挤出造粒， 加 工温度在 210-235 °C， 螺杆转数为 550rpm。
本发明还涉及到一种高耐磨尼龙 66复合材料及其制备方法。
实施例 10-15
该高耐磨尼龙 66 (PA66)复合材料以尼龙 66 (PA66)、 玻璃微珠（GB) 、 玻璃纤维粉 （GF) 以及润滑耐磨剂为主要材料， 其余为辅助材料。 该高耐磨 尼龙 66复合材料由以下组分和重量百分比的原料组成:
表 4: 配比 10-15
Figure imgf000012_0001
其中，该尼龙 66粘度为 2.4; 该玻璃微珠和玻璃纤维粉为无碱玻璃微珠和 无碱玻璃纤维粉， 其表面经硅垸偶联剂处理； 该超高分子量聚乙烯为第一润滑 耐磨剂， 该聚四氟乙烯为第二润滑耐磨剂； 该接枝型增韧改性剂为聚烯烃弹性 体 （POE ) 接枝不饱和酸或者酸酐的接枝聚合的低聚物， 其熔融指数为 1.0-5.0g/10mm,接枝率为 0.5-1 %。该抗氧剂为一种受阻酚类抗氧剂与亚磷酸酯 类抗氧剂的复配体系， 例如该抗氧剂为 1098/168 (重量比为 1 : 1 )， 1098 为 N,N'-1,6-亚己基-二 - [3,5-二叔丁基 -4-羟基苯丙酰胺]， 168为（2， 4 二叔丁基 苯基）亚磷酸三酯。 该润滑分散剂为硬脂酸钙， 还可为硬脂酸锌， 硬脂酸铝等 硬脂酸盐中的一种或者几种。该成核剂是以长碳链为主要成分的羧酸钙盐， 例 如市售成核剂 P-20, 该 P-20可以是德国科莱恩公司生产的。
将上述组分按比例放入高混机中混合 5-10分钟， 出料， 然后用螺杆挤出 机挤出造粒， 加工温度在 245-290°C， 螺杆转数在 400-600rpm。
表 5: 各段加热温度
Figure imgf000013_0001
根据实施例 10-15制得的样品 10-15， 进行性能测试对比， 采用 ASTM标 表 6: 测试性能对比
Figure imgf000013_0002
实施例 16
一种高耐磨 PA66复合材料的制备方法， 其制备方法如下： 歩骤一， 按重 量百分比称取的原料， PA66 占 69%， 表面经硅垸偶联剂处理的玻璃微珠占 10%, 表面经硅垸偶联剂处理的玻璃纤维粉占 10%, 第一润滑耐磨剂（超高分 子量聚乙烯） 占 3%， 第二润滑耐磨剂 （聚四氟乙烯） 占 3%， 接枝型增韧改 性剂占 4 %， 按照重量比为 1 : 1复配的抗氧剂 1098/168 复配体系占 0.5 %， 润滑分散剂硬脂酸钙占 0.2 %， 成核剂占 0.3 % ; 歩骤二， 将以上混合料放入高 混机中混合 5 分钟， 然后出料， 再用双螺杆挤出机挤出造粒， 加工温度在 250-265 °C , 螺杆转数在 600rpm。
该接枝型增韧改性剂为聚烯烃弹性体（POE)接枝不饱和酸或者酸酐的接 枝聚合的低聚物， 为马来酸酐接枝聚烯烃弹性体 （POE ) , 其熔融指数为 2g/10min, 接枝率为 0.5-1 %。
实施例 17
一种高耐磨 PA66复合材料的制备方法， 其制备方法如下： 歩骤一， 按重 量百分比称取的原料： PA66 占 73%， 表面经硅垸偶联剂处理的玻璃微珠占 10%, 表面经硅垸偶联剂处理的玻璃纤维粉占 10%, 第一润滑耐磨剂（超高分 子量聚乙烯） 占 3%， 第二润滑耐磨剂（聚四氟乙烯） 占 3%， 按照重量比为 1 : 1复配的抗氧剂 1098/168 复配体系占 0.3 %， 润滑分散剂硬脂酸钙占 0.2 %， 成核剂占 0.5 % ; 歩骤二： 将以上混合物放入高混机中混合 3分钟， 然后出料， 再用双螺杆挤出机挤出造粒， 加工温度在 245-270 °C， 螺杆转数在 550rpm。
实施例 18
一种高耐磨 PA66复合材料的制备方法， 其制备方法如下： 歩骤一， 按重 量百分比称取的原料， PA66 占 68.5%， 表面经硅垸偶联剂处理的玻璃微珠占 10%, 表面经硅垸偶联剂处理的玻璃纤维粉占 10%, 第一润滑耐磨剂（超高分 子量聚乙烯） 占 3%， 第二润滑耐磨剂 （聚四氟乙烯） 占 3%， 接枝型增韧改 性剂占 4 %， 按照重量比为 1 : 1复配的抗氧剂 1098/168 复配体系占 1 %， 润 滑分散剂硬脂酸钙占 0.2 %， 成核剂占 0.3 % ; 歩骤二， 将以上混合料放入高混 机中混合 5分钟，然后出料，再用双螺杆挤出机挤出造粒，加工温度在 250-265 °C， 螺杆转数在 600rpm。
本发明进一歩涉及到一种高耐磨尼龙 6/尼龙 66复合材料及其制备方法。 实施例 19-24
该高耐磨尼龙 6/尼龙 66复合材料以尼龙 6、 尼龙 66、 玻璃微珠、 玻璃纤 维粉以及润滑耐磨剂为主要材料， 其余为辅助材料。 该高耐磨尼龙 6/尼龙 66 复合材料由以下组分和重量百分比的原料组成：
表 7: 配比 19-24
Figure imgf000015_0001
该尼龙 6和尼龙 66的粘度为 2.4，该尼龙 66的粘度为 2.8。该玻璃微珠和 准
玻璃纤维粉为无碱玻璃微珠和无碱玻璃纤维粉， 其表面经硅垸偶联剂处理； 该 超高分子量聚乙烯为第一润滑耐磨剂， 该聚四氟乙烯为第二润滑耐磨剂； 该接 枝型增韧改性剂为聚烯烃弹性体（POE)接枝不饱和酸或者酸酐的接枝聚合的 低聚物， 其熔融指数为 1.0-5.0g/10min， 接枝率为 0.5-1 %。 该抗氧剂为一种受 阻酚类抗氧剂与亚磷酸酯类抗氧剂的复配体系，例如抗氧剂为 1098/168 (重量 比为 1 :1 )， 1098为 N,N'-1,6-亚己基 -二- [3,5-二叔丁基 -4-羟基苯丙酰胺]， 168 为 （2， 4 二叔丁基苯基） 亚磷酸三酯。 该润滑分散剂为硬脂酸钙， 还可为硬 脂酸锌，硬脂酸铝等硬脂酸盐中的一种或者几种。该成核剂是以长碳链为主要 成分的羧酸钙盐， 例如市售成核剂 P-20 , 该 P-20可以是德国科莱恩公司生产 的。
将上述组分按比例放入高混机中混合 5-10分钟， 出料， 然后用螺杆挤出 机挤出造粒， 加工温度在 235-280 °C， 螺杆转数在 400-600rpm。 螺杆组合为分 散性较好的特定组合。
表 8: 各段加热温度
Figure imgf000016_0001
根据实施例 19-24制得的样品 19-24， 进行性能测试对比， 采用 ASTM标 表 9: 测试性能对比
Figure imgf000016_0002
实施例 25
一种高耐磨 PA6/PA66复合材料的制备方法， 其制备方法如下： 按重量百 分比称取的原料： PA6为 39%， PA66为 30%， 表面经硅垸偶联剂处理的玻璃 微珠 10%， 表面经硅垸偶联剂处理的玻璃纤维粉 10%， 第一润滑耐磨剂 （超 高分子量聚乙烯） 3%， 第二润滑耐磨剂 （聚四氟乙烯） 3%， 接枝型增韧改 性剂 4 %， 按照重量比为 1 : 1复配的抗氧剂 1098/168 复配体系 0.5 %， 润滑 分散剂硬脂酸钙 0.2 %， 成核剂 0.3 %。 放入高混机中混合 5分钟， 出料， 然后 用双螺杆挤出机挤出造粒， 加工温度在 245-265 °C， 螺杆转数在 600rpm。
该接枝型增韧改性剂为聚烯烃弹性体（POE)接枝不饱和酸或者酸酐的接 枝聚合的低聚物， 为马来酸酐接枝聚烯烃弹性体 （POE ) , 其熔融指数为 2g/10min,接枝率为 0.5-1 %。
实施例 26
一种高耐磨 PA6/PA66复合材料的制备方法， 其制备方法如下： 按重量百 分比称取的原料： PA6 , 33%； PA66, 40%； 表面经硅垸偶联剂处理的玻璃微 珠， 10%; 表面经硅垸偶联剂处理的玻璃纤维粉， 10%; 第一润滑耐磨剂 （超 高分子量聚乙烯）， 3%； 第二润滑耐磨剂 （聚四氟乙烯）， 3%； 按照重量比为 1： 1复配的抗氧剂 1098/168 复配体系， 0.3 % ; 润滑分散剂硬脂酸钙， 0.2 % ; 成核剂， 0.5 %。 放入高混机中混合 3 分钟， 出料， 然后用双螺杆挤出机挤出 造粒， 加工温度在 245-275°C， 螺杆转数在 550rpm。
实施例 27
一种高耐磨 PA6/PA66复合材料的制备方法， 其制备方法如下： 按重量百 分比称取的原料： PA6为 38.3%， PA66为 30%， 表面经硅垸偶联剂处理的玻 璃微珠 10%,表面经硅垸偶联剂处理的玻璃纤维粉 10%,第一润滑耐磨剂（超 高分子量聚乙烯） 3%， 第二润滑耐磨剂 （聚四氟乙烯） 3%， 接枝型增韧改性 剂 4 %， 按照重量比为 1 : 1复配的抗氧剂 1098/168 复配体系 1 %， 润滑分散 剂硬脂酸钙 0.2 %， 成核剂 0.5 %。放入高混机中混合 5分钟， 出料， 然后用双 螺杆挤出机挤出造粒， 加工温度在 245-265 °C， 螺杆转数在 600rpm。
实施例 28-33
一种高耐磨 PA6/PA66复合材料， 该复合材料由以下组分和重量百分比的 表 10: 配比 28-33
Figure imgf000018_0001
将上述组分按比例放入高混机中混合 5-10分钟， 出料， 然后用螺杆挤出 机挤出造粒， 加工温度在 235-280 °C， 螺杆转数在 400-600rpm。 螺杆组合为分 散性较好的特定组合。
实施例 34-41
一种高耐磨 PA6/PA66 复合材料， 该复合材料由以下组分和重量百分比 (wt%) 的原料组成：
表 10: 配比 34-41
Figure imgf000018_0002
聚四氟乙烯
0 5 4 3 3 0 4 3.5
(PTFE)
接枝型增韧改性
剂 3 5 4 4 0 3 3 3
(POE-g-MAH)
抗氧剂
0 0 0.3 1 1 0 0.5 0.5 1098/168 ( 1： 1 ) 润滑分散剂
0 0 0 0 0.2 0.3 0 0
(硬脂酸钙）
成核剂 (P-20) 0 0 0 0 0 0 0.2 0.5 将上述组分按比例放入高混机中混合 5-10分钟， 出料， 然后用螺杆挤出 机挤出造粒， 加工温度在 235-280 °C， 螺杆转数在 400-600rpm。 螺杆组合为分 散性较好的特定组合。
本发明还提供了采用高耐磨尼龙 6(PA6)、 尼龙 66(PA66)、 尼龙 6(ΡΑ6)/尼 龙 66(ΡΑ66)复合材料制成的滚轮，该滚轮用于机场货物中转运输车的升降平台 式装置。 如图 1所示， 该滚轮 110中心横穿有轴孔 111， 滚轮旋转轴可以装设 该轴孔 111 中， 且通过该滚轮旋转轴固定该滚轮轴架上， 用于运输。 该滚轮 110的前后两端 112设置有平面结构， 使其与其它轨道相互配合。 该滚轮 110 的外表面 113是磨砂质感，在运送物体时增大滚轮与集装箱底板和集装板底板 摩擦力。 该尼龙材质滚轮 110用尼龙材质制成， 经久耐用， 不易磨损， 而且不 打滑。本发明尼龙材质的滚轮选用材质设计十分合理， 尤其是在任何环境及天 气下运送物体时控制自如，滚轮与集装箱底板和集装板底板摩擦力增大， 不易 打滑， 传动时摩擦不易产生噪音， 不易磨损， 噪音很小， 且符合环保等特点。 该滚轮耐用， 韧性好、 坚硬度特强， 能承受较大冲击力， 除了该材质已有防滑 作用外， 磨沙质感外表更能额外提供防滑性。避免金属和金属转动时粉末的剥 落， 对环境造成污染， 避免金属粉末进入眼睛和呼吸道对人体造成伤害。减少 金属和金属传输摩擦时所产生的剌耳声和震动的噪音， 减少对人体耳朵的损 害， 且物美价廉。 可以理解的是， 利用本发明的高耐磨尼龙 6 PA6;>、 尼龙 66 PA66;>、 尼龙 6(PA6)/尼龙 66(PA66)复合材料还可以制成其他的产品可广泛应用于汽车、 机 械设备连接件、 齿轮、 油田设备、 仪器仪表、 纺织设备、 电子电器设备、 以及 家用电器等中。
以上所述仅为本发明的较佳实施方式，凡依本发明权利要求范围所做的均 等变化与修饰， 皆应属本发明权利要求的涵盖范围。

Claims

权 利 要 求 书
1、 用于机场货运车滚轮的高耐磨尼龙复合材料， 其特征在于： 它是由下 重量配比的组分制成的复合材料：
尼龙 6， 60-80%；
玻璃微珠， 5-13%;
玻璃纤维粉， 6-14%;
润滑耐磨剂， 5-7 % ;
接枝型增韧改性剂， 3-5%;
抗氧剂， 0.3-1%;
润滑分散剂， 0.2-0.3%;
成核剂， 0.2-0.5%。
2、 用于机场货运车滚轮的高耐磨尼龙复合材料， 其特征在于： 它是由下 重量配比的组分制成的复合材料：
尼龙 66， 60-80%；
玻璃微珠， 5-13%;
玻璃纤维粉， 6-14%;
润滑耐磨剂， 5-7 % ;
接枝型增韧改性剂， 3-5%;
抗氧剂， 0.3-1%;
润滑分散剂， 0.2-0.3%;
成核剂， 0.2-0.5%。
3、 用于机场货运车滚轮的高耐磨尼龙复合材料， 其特征在于： 它是由下 重量配比的组分制成的复合材料：
尼龙 6， 18-41%；
尼龙 66， 28-42%；
玻璃微珠， 5-13%; 玻璃纤维粉， 6-14%;
润滑耐磨剂， 5-7 % ;
接枝型增韧改性剂， 3-5%;
抗氧剂， 0.3-1%;
润滑分散剂， 0.2-0.3%;
成核剂， 0.2-0.5%。
4、 用于机场货运车滚轮的高耐磨尼龙复合材料， 其特征在于： 它是由下 述重量配比的组分制成的复合材料：
尼龙 6或者尼龙 66或者尼龙 6与尼龙 66的混合物， 60-80%;
玻璃微珠， 5-16%;
玻璃纤维粉， 6-18%;
润滑耐磨剂， 5-7 %。
5、 根据权利要求 1至 4任意一项所述的用于机场货运车滚轮的高耐磨尼 龙复合材料， 其特征在于： 所述润滑耐磨剂为超高分子量聚乙烯， 或者为聚四 氟乙烯， 或者超高分子量聚乙烯与聚四氟乙烯的混合物。
6、 根据权利要求 1至 4任意一项所述的用于机场货运车滚轮的高耐磨尼 龙复合材料， 其特征在于： 所述玻璃微珠和玻璃纤维粉的表面经过硅垸偶联剂 处理。
7、 根据权利要求 4所述的用于机场货运车滚轮的高耐磨尼龙复合材料， 其特征在于： 所述高耐磨尼龙复合材料的组分还包括接枝型增韧改性剂。
8、 根据权利要求 7所述的用于机场货运车滚轮的高耐磨尼龙复合材料， 其特征在于： 所述接枝型增韧改性剂的含量为重量比为 3-5 %。
9、 根据权利要求 1或 2或 3或 7或 8所述的用于机场货运车滚轮的高耐 磨尼龙复合材料， 其特征在于：所述接枝型增韧改性剂为聚烯烃弹性体接枝不 饱和酸或者酸酐的接枝聚合的低聚物， 其熔融指数为 1.0-5.0g/10mm， 接枝率 为 0.5-1 %。
10、 根据权利要求 9所述的用于机场货运车滚轮的高耐磨尼龙复合材料， 其特征在于：所述聚烯烃弹性体接枝不饱和酸或者酸酐的接枝聚合的低聚物为 马来酸酐接枝聚烯烃弹性体， 其熔融指数为 2g/10mm， 接枝率为 0.8 %。
11、 根据权利要求 4所述的用于机场货运车滚轮的高耐磨尼龙复合材料， 其特征在于： 所述高耐磨尼龙复合材料的组分还包括抗氧剂。
12、根据权利要求 11所述的用于机场货运车滚轮的高耐磨尼龙复合材料， 其特征在于： 所述抗氧剂含量为重量比 0.3-1 %。
13、根据权利要求 1或 2或 3或 11或 12所述的用于机场货运车滚轮的高 耐磨尼龙复合材料， 其特征在于：所述抗氧剂为一种受阻酚类抗氧剂与亚磷酸 酯类抗氧剂的复配体系。
14、根据权利要求 13所述的用于机场货运车滚轮的高耐磨尼龙复合材料， 其特征在于：所述受阻酚类抗氧剂与亚磷酸酯类抗氧剂的复配体系为重量比为 1： 1的抗氧剂 1098与抗氧剂 168。
15、 根据权利要求 4所述的用于机场货运车滚轮的高耐磨尼龙复合材料， 其特征在于： 所述高耐磨尼龙复合材料的组分还包括润滑分散剂。
16、根据权利要求 15所述的用于机场货运车滚轮的高耐磨尼龙复合材料， 其特征在于： 所述润滑分散剂的含量为重量比 0.2-0.3 %。
17、根据权利要求 1或 2或 3或 15或 16所述的用于机场货运车滚轮的高 耐磨尼龙复合材料， 其特征在于： 所述润滑分散剂为硬脂酸盐。
18、根据权利要求 17所述的用于机场货运车滚轮的高耐磨尼龙复合材料， 其特征在于： 所述硬脂酸盐选自硬脂酸钙， 硬脂酸锌， 硬脂酸铝中的一种或者 几种。
19、 根据权利要求 4所述的用于机场货运车滚轮的高耐磨尼龙复合材料， 其特征在于： 所述高耐磨尼龙复合材料的组分还包括成核剂。
20、根据权利要求 19所述的用于机场货运车滚轮的高耐磨尼龙复合材料， 其特征在于： 所述成核剂的含量为重量比 0.2-0.5 %。
21、根据权利要求 1或 2或 3或 19或 20所述的用于机场货运车滚轮的高 耐磨尼龙复合材料， 其特征在于： 所述成核剂为市售成核剂 P-20。
22、 根据权利要求 4所述的用于机场货运车滚轮的高耐磨尼龙复合材料， 其特征在于： 各组分的重量配比为：
尼龙 6或者尼龙 66或者尼龙 6与尼龙 66的混合物， 69-73%;
玻璃微珠， 5-12%;
玻璃纤维粉， 10-17%;
润滑耐磨剂， 5-6 %。
23、如权利要求 1所述的用于机场货运车滚轮的高耐磨尼龙复合材料的制 备方法，其特征在于：歩骤一，先按以下重量百分比称取原料，尼龙 6， 60-80%； 玻璃微珠， 5-13%; 玻璃纤维粉， 6-14%; 润滑耐磨剂， 5-7 % ; 接枝型增韧改 性剂， 3-5 %； 抗氧剂， 0.3-1 %； 润滑分散剂， 0.2-0.3 %； 成核剂， 0.2-0.5 %； 歩骤二，将以上原料放入高混机中混合均匀，然后出料，再用挤出机挤出造粒， 加工温度为 210°C-290°C。
24、如权利要求 2所述的用于机场货运车滚轮的高耐磨尼龙复合材料的制 备方法，其特征在于：歩骤一，先按以下重量百分比称取原料，尼龙 66， 60-80%； 玻璃微珠， 5-13%; 玻璃纤维粉， 6-14%; 润滑耐磨剂， 5-7 % ; 接枝型增韧改 性剂， 3-5 %； 抗氧剂， 0.3-1 %； 润滑分散剂， 0.2-0.3 %； 成核剂， 0.2-0.5 %； 歩骤二，将以上原料放入高混机中混合均匀，然后出料，再用挤出机挤出造粒， 加工温度为 210°C-290°C。
25、如权利要求 3所述的用于机场货运车滚轮的高耐磨尼龙复合材料的制 备方法，其特征在于：歩骤一，先按以下重量百分比称取原料，尼龙 6， 18-41%; 尼龙 66， 28-42%； 玻璃微珠， 5-13%; 玻璃纤维粉， 6-14%; 润滑耐磨剂， 5-7 %； 接枝型增韧改性剂， 3-5 %； 抗氧剂， 0.3-1 %； 润滑分散剂， 0.2-0.3 %； 成核剂占 0.2-0.5 % ; 歩骤二， 将以上原料放入高混机中混合均匀， 然后出料， 再用挤出机挤出造粒， 加工温度为 210°C-290°C。
26、如权利要求 4所述的用于机场货运车滚轮的高耐磨尼龙复合材料的制 备方法， 其特征在于： 歩骤一， 先按以下重量百分比称取原料， 尼龙 6或者尼 龙 66或者尼龙 6和尼龙 66的混合物， 60-80%; 玻璃微珠， 5-16%; 玻璃纤维 粉， 6-18%; 润滑耐磨剂， 5-7%; 歩骤二， 将以上原料放入高混机中混合均匀: 然后出料， 再用挤出机挤出造粒， 加工温度为 210°C-290°C。
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