CN103980595A - Modified ultrahigh molecular polyethylene for 3D printing and preparation method thereof - Google Patents
Modified ultrahigh molecular polyethylene for 3D printing and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- 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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Abstract
A modified ultrahigh molecular polyethylene material for 3D printing comprises the following components, by weight, 80-95 parts of ultrahigh molecular polyethylene, 30-40 parts of low-density polyethylene, 10-15 parts of carbon nanotube, 1-10 parts of an inorganic filling material, 1-5 parts of a modifier, 0.1-0.5 part of an antioxidant and 0.1-0.5 part of a coupling agent. The modified UHMWPE material provided by the invention has good melt fluidity, heat resistance and abrasion resistance. By the preparation method, the ultrahigh molecular polyethylene is more in line with characteristics of a 3D printing material, and the ultrahigh molecular polyethylene has a wide application prospect in the 3D printing technology.
Description
Technical field
The present invention relates to a kind of modified ultra-high molecular weight polyethylene material and preparation method thereof, be specifically related to a kind of modified ultra-high molecular weight polyethylene material of printing for 3D and preparation method thereof.
Background technology
3D printing technique mainly comprises the techniques such as SLA, FDM, SLS, LOM.Wherein fusion sediment forming technique (FDM) and selective laser sintering (SLS) technology are all used thermoplastics as basic 3D printed material.
As a kind of high thermoplastic engineering plastic of molecular weight with linear structure, molecular structure and the common polythene material of ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) are basic identical.But UHMWPE has the performances such as shock-resistant, wear-resistant, the self lubricity, resistance to chemical attack of the unrivaled excellence of other plastics because molecular weight is high.And UHMWPE resistance to low temperature is excellent, still has higher shock strength in the time of-40 ℃, even can at-269 ℃, use.The Physical Mechanical of UHMWPE excellence makes it can be widely used in the fields such as machinery, transportation, weaving, papermaking, mining industry, building, military affairs, agricultural, chemical industry and sports movement apparatus, wherein being most widely used with heavy packages container and pipeline.In addition, due to the physiology inertia of UHMWPE excellence, it uses in clinical medicine as heart valve, orthopedics's part, joint prosthesis etc.
Although UHMWPE has the characteristic of many excellences, also there are many deficiencies.UHMWPE has high molecular weight, and its molecular chain is very long, extremely long molecular chain mutually entanglement can to cause its melt be elastomeric high viscosity elastomerics, mobility is very poor, and shear fracture phenomenon easily occurs.Melt flow rate (MFR) (MFR) low (almost nil), fusing point high (190-210 ℃), viscosity greatly, extremely difficult machine-shaping etc.Compare with Other Engineering plastics in addition, have that surface hardness is low, heat-drawn wire is low, flexural strength and the shortcoming such as creep resistant is poor, antiwear property is poor, intensity is low, it is very difficult that thereby the forming process that makes UHMWPE becomes, seriously hinder its application, made it not satisfactory as 3D printed material.
CN1433443A relates to a kind of method that embeds the complex body of nanofiber in polymeric matrix that is formed on, the method is included in sneaks into nanofiber to form coacervate in plastic substrate, and by diplomatic corps's aggressiveness under hydrodynamic force stress and the nanofiber that distributes equably; Described hydrodynamic force stress splits off described coacervate, in conjunction with carrying out extra extension, flows and can be used to realize minor diameter and arrangement.Gained complex body can deposit with consolidation (FDM) moulding, and the polymkeric substance wherein a volume nanofiber being strengthened is as the wire raw material of FDM technique.In this process, nanofiber complex line (diameter is about 2 millimeters) is extruded through the die head of mm size, produces complex line in a row and makes sheet material and 3D parts.In this patent, raw material used is the polymkeric substance wire rod that nanofiber strengthens.Its shortcoming is: the FDM of nanofiber complex line is very complicated, is difficult for processing.
CN1812878A relates to a kind of powder of the 3D of being suitable for printing, and this powder comprises the blend of thermoplastic granulates thing and adhesive particle thing, and wherein said thermoplastic granulates thing is optional from polyolefine.The powder of this patent, when printing for 3D, need to be used solvent.Therefore, the 3D printing system of CN1812878A is liquid composition, and its shortcoming is to need to use in many cases to the mankind and harmful solvent or the dispersion agent of environment, and complicated operation, is difficult for dispersed or dissolves.
CN102093646A relates to a kind of material of printing rapid shaping for 3D and preparation method thereof, rapid prototyping material comprises modified powder materials A and binding agent B, wherein: the preparation of modified powder materials A: powdered material and the first solvent are joined to ball mill or grinding machine for grinding, obtain powdered material pre-treatment material; By tensio-active agent, lubricant, organic resin successively joins in the second solvent, and dispersed with stirring 2-3h, obtains modification liquid; Powdered material pre-treatment material is mixed with modification liquid, put into shredder, normal temperature mixed grinding, dry, grind, obtain modified powder materials A; During use, 1 part of modified powder materials A and 0.01-0.07 part binding agent B adapted.This patent 3D formed body used is solution system, and its shortcoming is to prepare in materials process needs material to grind and modification, and uses supercritical drying, complicated operation.
US2004/0232583A1 relates to a kind of method of manufacturing three-dimensional body, and it comprises: a powdered substrate layer a) is provided; B) on one or more regions of described base material, selectivity applies at least one microwave absorbing first sensitive materials; C) with layer described in microwave radiation processing at least one times.Wherein loosely mention and can use the polymkeric substance that is selected from polyester, polyvinyl chloride, polyacetal, polypropylene, polyethylene, polystyrene, polycarbonate, PMMI, PMMA, ionomer, polymeric amide, copolyesters, copolyamide, terpolymer, ABS or its mixture.US2004/0232583A1 does not mention polyethylene is carried out to modification, so that it is suitable for 3D printing.
US3,847,888 relate to a kind of ultrahigh molecular weight linear polyethylene, and its molecular weight is at least 1 * 10
6, density is 0.92-0.99.Its not mentioned described ultrahigh molecular weight linear polyethylene application in 3D printed material.
Prior art is all not mentioned carries out modification so that be suitable for 3D printing to ultrahigh molecular weight polyethylene(UHMWPE).Therefore, the object of the invention is at present its melt flow rate (MFR) is low, viscosity large, poor fluidity and extremely difficult by features such as injection moulding process machine-shapings, propose a kind of method of fluidity of molten of the UHMWPE of improvement material.By adding appropriate Low Density Polyethylene, flow ability modifying agent, coupling agent and mineral filler etc. to improve the fluidity of molten of material, improve the mechanical propertys such as its thermotolerance, wearability simultaneously.The MFR value of the material of gained is greater than 2g/10min (experimental technique carries out according to GB/T3682-2000 (ISO1133)) by almost nil bringing up to, and makes it be suitable for use as 3D printed material.
Summary of the invention
The present invention relates to a kind of modified ultra-high molecular weight polyethylene material of printing for 3D, the following component that it comprises by weight, preferably consists of following component:
The commercially available acquisition of described ultrahigh molecular weight polyethylene(UHMWPE), its molecular weight can be greater than 1,500,000, for example, be 150-300 ten thousand, and density is at 0.93-0.96g/cm
3between, heat-drawn wire is 85-90 ℃.The consumption of described ultrahigh molecular weight polyethylene(UHMWPE) is preferably 82-92 part, more preferably 85-90 part.
Described Low Density Polyethylene is the polyethylene that high pressure polymerisation produces, its commercially available acquisition, and its density is generally 0.93-0.95g/cm
3, melt index is generally 2.0-2.10g/10min.The consumption of described Low Density Polyethylene is preferably 30-38 part, more preferably 30-35 part.
Described carbon nanotube can be various carbon nanotubes, for example Single Walled Carbon Nanotube, multi-walled carbon nano-tubes.The inventor finds surprisingly, with ordinary method nitric acid, described carbon nanotube is activated, and nitric acid activation energy increases its specific surface area greatly, and can improve avtive spot, improves the dispersiveness in matrix.The concrete technology of nitric acid activation can be carbon nanotube backflow 2h-2.5h in concentrated nitric acid (65%), disperses (for example stirring, ultrasonic dispersion, preferred ultrasonic dispersion) simultaneously, then with distilled water, is washed till neutrality.The consumption of described carbon nanotube is preferably 10-14 part, more preferably 10-13 part.
Described mineral filler is selected from molybdenumdisulphide, glass microballon, talcum powder, super-fine silicon micro-powder.Preferably, described molybdenumdisulphide is the molybdenumdisulphide particle with 1000-1500 order granularity.Preferably, described glass microballon is for having 10-50 micron granularity, the glass microballon of 1-2 micron wall thickness.Preferably, to be not less than be 5000 object talcum powder to described talcum powder fineness.Preferably, the particle diameter of described super-fine silicon micro-powder is 0.1-0.3 micron.The consumption of described mineral filler is preferably 1-8 part, more preferably 1-5 part.
Described properties-correcting agent is selected from polyester or poly-(methyl) acrylate.Described polyester is for example polyethylene terephthalate (PET), polybutylene terephthalate (PBT), PEN (PEN) or PBN (PBN).Described poly-(methyl) acrylate can be poly-(methyl) methyl acrylate, poly-(methyl) ethyl propenoate, poly-(methyl) propyl acrylate, poly-(methyl) butyl acrylate, poly-(methyl) cyclohexyl acrylate etc.The consumption of described properties-correcting agent is preferably 1-4 part, more preferably 1-3 part.
In preferred embodiments, modified ultra-high molecular weight polyethylene material of the present invention also contains oxidation inhibitor.Preferably, described oxidation inhibitor is antioxidant CA.Its consumption is 0.1-0.5 part, is preferably 0.1-0.4 part.
In another preferred embodiment, modified ultra-high molecular weight polyethylene material of the present invention also contains coupling agent.Described coupling agent is selected from titanic acid ester, silane.Titanic acid ester can be sec.-propyl three (isostearoyl base) titanic acid ester, sec.-propyl three (dioctyl pyrophosphate) titanic acid ester or two (dioctyl pyrophosphoryl base) containing fluoroacetic acid ester titanium, is preferably sec.-propyl three (isostearoyl base) titanic acid ester.Described silane is preferably KH-550 type silane coupling agent.Selected coupling agent can reduce the viscosity of molten synthetic resin, improves the dispersity of weighting agent to improve processing characteristics, and then makes goods obtain good surface quality and machinery, heat and electrical property.The consumption of described coupling agent is 0.1-0.5 part, is preferably 0.1-0.4 part.
In one aspect of the invention, also relate to the purposes of modified ultra-high molecular weight polyethylene material of the present invention in 3D prints.
In another aspect of this invention, also relate to a kind of 3D Method of printing, it is characterized in that using modified ultra-high molecular weight polyethylene material of the present invention.
The invention still further relates to a kind of method of preparing the modified ultra-high molecular weight polyethylene material of printing for 3D of the present invention, it is characterized in that each component extruding pelletization.
The inventor finds surprisingly, if first mineral filler is mixed with the solution of properties-correcting agent and coupling agent, then the mixture of gained is mixed with other components of matrix material of the present invention after dry, and by the mixture extruding pelletization of gained, obtain and there is homodisperse matrix material thus, and the matrix material of gained has excellent melt flow rate (MFR), be very suitable for 3D and print.
More specifically, described method has following processing step:
1) mineral filler is dispersed in dispersion medium, then adds properties-correcting agent and coupling agent, disperse and be dried;
2) by supramolecule weight northylen, Low Density Polyethylene, carbon nanotube, in step 1) in the mineral filler and the oxidation inhibitor that obtain mix;
3) will be in step 2) in the extruding pelletization that obtains, thereby obtain modified ultra-high molecular weight polyethylene material.
In step 1) in, in being dispersed to dispersion medium before, preferably that mineral filler is dry.Step 1) in, dispersion medium used can be ethanol, water, acetone, is preferably ethanol.Described dispersion can be undertaken by stirring, ultrasonic dispersion, preferably by ultrasonic dispersion, is undertaken.
In step 2) in, described mixing can be carried out in high-speed mixer.
Step 3) extruding pelletization in can be used single screw extrusion machine or twin screw extruder to carry out.In the situation that using twin screw extruder, procession parameters is: opening for feed is followed successively by 230-240,240-250,250-260,250-260,240-250,240-250 ℃ to each section of temperature distribution of machine barrel of mouthful mould, and engine speed is 300-350r/min.
In preferred embodiments, the invention still further relates to a kind of method of preparing the modified ultra-high molecular weight polyethylene material of printing for 3D of the present invention, it is characterized in that described method comprises following processing step:
1) first that mineral filler is dry, be dispersed in dispersion medium, stir, under agitation add in proportion properties-correcting agent and coupling agent, then stir.Then vibrating dispersion in ultra-sonic oscillation instrument, dries to constant weight.
2), by supramolecule weight northylen, Low Density Polyethylene, carbon nanotube, in step 1) in the mixture of mineral filler, properties-correcting agent and coupling agent of gained, oxidation inhibitor mixes in proportion in high-speed mixer.
3) by step 2) middle extruding pelletization, thus obtain modified UHMWPE.
Preferably, the preparation technology of described modified ultra-high molecular weight polyethylene material is as follows:
1) first mineral filler is dried to 4 hours at 160 ℃, after weighing, is dispersed in ethanol medium, by electric blender, stir 30 minutes to evenly, properties-correcting agent, coupling agent are added in dispersion medium in proportion, then stir 30 minutes to even.Then in ultra-sonic oscillation instrument, vibrating dispersion, after 1 hour, is dried to constant weight, standby.
2) by supramolecule weight northylen, Low Density Polyethylene, carbon nanotube, step 1) in obtain mineral filler,, oxidation inhibitor, join in high-speed mixer and mix.
3) by step 2) in material after mixing add extruding pelletization in twin screw extruder to make modified UHMWPE pellet.Procession parameters: opening for feed is to machine barrel each section of temperature distribution 230-240,240-250,250-260,250-260,240-250, the 240-250 ℃ of mouthful mould, and engine speed is 300r/min.
In order to test, the pellet also step 3 being obtained is injection molded into standard test specimen through injection moulding machine.Shooting Technique parameter: barrel zone temperature each section of temperature distribution of machine barrel from opening for feed to mouthful mould is followed successively by 200-210,210-220,220-230,230-240,240-250,245-255 ℃; Injection pressure 45MPa; Injection speed (indicated airspeed) 30cm
3/ s; Inject time 4s; Cooling time 11s.
The outstanding feature of the present invention is:
1. modified UHMWPE material of the present invention has good fluidity of molten (>2g/10min), thereby make to be very suitable for 3D, prints.
2. modified UHMWPE material of the present invention has high heat resistance, wearability.
3. production cost of the present invention is low, and production process is simple, is easy to suitability for industrialized production.
Embodiment
Below by embodiment, the present invention is described in further detail, but this should be interpreted as to scope of the present invention only limits to following embodiment.In the situation that not departing from aforesaid method thought of the present invention, various replacements or the change according to ordinary skill knowledge and customary means, made, all should be within the scope of the present invention.
Except as otherwise noted, otherwise the present invention's " part " used and percentage ratio all based on weight.
MFR test is carried out according to GSB15-1312-2012, cantilever beam impact strength, the test of socle girder notched Izod impact strength are carried out according to GB1043-79, tensile strength is carried out according to GBT1040-2006, elongation at break test is carried out according to ISO6239, heat-drawn wire test is carried out according to GB/T1633-2000, and PVvalue testing is carried out according to GB10006-1988.In embodiment below, carbon nanotube used is that concrete technology is as follows: by carbon nanotube backflow 2h in concentrated nitric acid (65%), carry out ultrasonic dispersion simultaneously, then with distilled water, be washed till neutrality with the carbon nanotube of nitric acid activation.
Embodiment 1
1) first molybdenumdisulphide is dried to 4 hours at 160 ℃; after weighing, be dispersed in ethanol medium; by electric blender, stir 30 minutes to even; 5 parts of properties-correcting agent polymethylmethacrylates, 0.2 part of coupling agent sec.-propyl three (isostearoyl base) titanic acid ester are added in dispersion medium, then stir 30 minutes to even.Then in ultra-sonic oscillation instrument, vibrating dispersion, after 1 hour, is dried to constant weight, standby.
2) by the UHMWPE of 95 weight parts, 30 parts of Low Density Polyethylenes, 10 parts carbon nanotube, 5 parts molybdenumdisulphide, 0.1 part antioxidant CA and in step 1) in the product of gained join in high-speed mixer and mix, fully discharging after mixed grinding reaction 1h.
3) by step 2) in the compound that obtains to add length-to-diameter ratio be that in 36 twin screw extruder, extruding pelletization is made UHMWPE pellet.The time that material stops in forcing machine is 3 minutes.Extruder temperature is set as successively: opening for feed is to 230,240,250,250,240,240 ℃ of each section of temperature distribution of machine barrel of mouthful mould, and engine speed is 300r/min.
4) by step 3) in the pellet that obtains through injection moulding machine, be injection molded into standard test specimen.Shooting Technique parameter: opening for feed is 200,210,220,230,240,245 ℃ to each section of temperature distribution of machine barrel of mouthful mould; Injection pressure 45MPa; Injection speed (indicated airspeed) 30cm
3/ s; Inject time 4s; Cooling time 11s.
The salient features of UHMWPE-1 after pure UHMWPE and modification is detected, and its detected result is as follows:
| Test item | Pure UHMWPE | Modified UHMWPE-1 |
| MFR/(10min) -1 | 0 | 2.54 |
| Cantilever beam impact strength/kJm -2 | Do not rupture | 90 |
| Socle girder notched Izod impact strength/kJm -2 | 10 | 70 |
| Tensile strength/MPa | 34 | 22 |
| Elongation at break/% | 350 | 380 |
| Heat-drawn wire/℃ | 85 | 80 |
| Frictional coefficient | 0.07 | 0.32 |
Embodiment 2
1) UHMWPE of 90 weight parts, 35 parts of Low Density Polyethylenes, the carbon nanotube of 10 parts, the talcum powder of 10 parts, the polymethylmethacrylate of 2 parts, antioxidant CA, 0.5 part of sec.-propyl three (isostearoyl base) titanic acid ester of 0.5 part are joined in high-speed mixer and mixed, fully discharging after mixed grinding reaction 1h.
2) by step 1) in the compound that obtains to add length-to-diameter ratio be that in 36 twin screw extruder, extruding pelletization is made UHMWPE pellet.The time that material stops in forcing machine is 5 minutes.Extruder temperature is set as successively: opening for feed is 235,245,250,255,240,240 ℃ to each section of temperature distribution of machine barrel of mouthful mould, and engine speed is 300r/min.
3) pellet step 3 being obtained is injection molded into standard test specimen through injection moulding machine.Shooting Technique parameter: opening for feed is 205,215,220,235,240,250 ℃ to each section of temperature distribution of machine barrel of mouthful mould; Injection pressure 45MPa; Injection speed (indicated airspeed) 30cm
3/ s; Inject time 4s; Cooling time 11s.
The salient features of UHMWPE-2 after pure UHMWPE and modification is detected, and its detected result is as follows:
| Test item | Pure UHMWPE | Modified UHMWPE-2 |
| MFR/(10min) -1 | 0 | 2.04 |
| Cantilever beam impact strength/kJm -2 | Do not rupture | 88 |
| Socle girder notched Izod impact strength/kJm -2 | 10 | 62 |
| Tensile strength/MPa | 34 | 22 |
| Elongation at break/% | 350 | 410 |
| Heat-drawn wire/℃ | 85 | 83.2 |
| Frictional coefficient | 0.09 | 0.25 |
Embodiment 3
1) UHMWPE of 95 weight parts, 40 parts of Low Density Polyethylenes, the carbon nanotube of 15 parts, 10 parts of glass microballons, 3 parts of polymethylmethacrylates, 0.5 part of antioxidant CA, 0.5 part of silane are joined in high-speed mixer and mixed, fully discharging after mixed grinding reaction 1h.
2) by step 1) in the compound that obtains to add length-to-diameter ratio be that in 36 twin screw extruder, extruding pelletization is made UHMWPE pellet.The time that material stops in forcing machine is 5 minutes.Extruder temperature is set as successively: opening for feed is 240,250,260,260,250,250 ℃ to each section of temperature distribution of machine barrel of mouthful mould, and engine speed is 300r/min.
3) pellet step 3 being obtained is injection molded into standard test specimen through injection moulding machine.Shooting Technique parameter: opening for feed is 210,220,230,240,250,255 ℃ to each section of temperature distribution of machine barrel of mouthful mould; Injection pressure 45MPa; Injection speed (indicated airspeed) 30cm
3/ s; Inject time 4s; Cooling time 11s.
The salient features of UHMWPE-3 after pure UHMWPE and modification is detected to its inspection
Result is as follows:
| Test item | Pure UHMWPE | Modified UHMWPE-3 |
| MFR/(10min) -1 | 0 | 2.45 |
| Cantilever beam impact strength/kJm -2 | Do not rupture | 92 |
| Socle girder notched Izod impact strength/kJm -2 | 10 | 67 |
| Tensile strength/MPa | 34 | 24 |
| Elongation at break/% | 350 | 385 |
| Heat-drawn wire/℃ | 85 | 80 |
| Frictional coefficient | 0.10 | 0.28 |
Embodiment 4
1) UHMWPE of 80 weight parts, 40 parts of Low Density Polyethylenes, the carbon nanotube of 15 parts, the silicon powder of 10 parts, poly-(methyl) ethyl propenoate of 5 parts, the antioxidant CA of 0.3 part, the silane of 0.1 part are joined in high-speed mixer and mixed, fully discharging after mixed grinding reaction 1h.
2) by step 1) in the compound that obtains to add length-to-diameter ratio be that in 36 twin screw extruder, extruding pelletization is made UHMWPE pellet.The time that material stops in forcing machine is 3 minutes.Extruder temperature is set as successively: opening for feed is 235,250,255,260,250,250 ℃ to each section of temperature distribution of machine barrel of mouthful mould, and engine speed is 300r/min.
3) pellet step 3 being obtained is injection molded into standard test specimen through injection moulding machine.Shooting Technique parameter: opening for feed is 200,215,230,235,240,255 ℃ to each section of temperature distribution of machine barrel of mouthful mould; Injection pressure 45MPa; Injection speed (indicated airspeed) 30cm
3/ s; Inject time 4s; Cooling time 11s.
The salient features of UHMWPE-4 after pure UHMWPE and modification is detected to its inspection
Result is as follows:
| Test item | Pure UHMWPE | Modified UHMWPE-4 |
| MFR/(10min) -1 | 0 | 3.36 |
| Cantilever beam impact strength/kJm -2 | Do not rupture | 98 |
| Socle girder notched Izod impact strength/kJm -2 | 10 | 69 |
| Tensile strength/MPa | 34 | 24 |
| Elongation at break/% | 350 | 421 |
| Heat-drawn wire/℃ | 85 | 74 |
| Frictional coefficient | 0.10 | 0.26 |
As seen from the above embodiment, by the fluidity of molten that adds appropriate Low Density Polyethylene, flow ability modifying agent, coupling agent and mineral filler etc. to improve to a great extent, improve the mechanical propertys such as its thermotolerance, wearability simultaneously, make it be suitable for use as 3D printed material.
Claims (10)
1. a modified ultra-high molecular weight polyethylene material, it comprises following component by weight:
2. according to the modified ultra-high molecular weight polyethylene material of claim 1, it is characterized in that described carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
Preferably, it is characterized in that described carbon nanotube activates with nitric acid.
3. according to the modified ultra-high molecular weight polyethylene material of any one in claim 1-2, it is characterized in that described mineral filler is selected from molybdenumdisulphide, glass microballon, talcum powder or super-fine silicon micro-powder.
4. according to the modified ultra-high molecular weight polyethylene material of any one in claim 1-3, it is characterized in that described properties-correcting agent is selected from polyester or poly-(methyl) acrylate.
5. according to the modified ultra-high molecular weight polyethylene material of any one in claim 1-4, it is characterized in that described modified ultra-high molecular weight polyethylene material also contains oxidation inhibitor.
6. according to the modified ultra-high molecular weight polyethylene material of any one in claim 1-5, it is characterized in that described modified ultra-high molecular weight polyethylene material also contains coupling agent.
7. prepare according to a method for the modified ultra-high molecular weight polyethylene material of any one in claim 1-6, it is characterized in that described method comprises each component extruding pelletization.
8. a method of preparing modified ultra-high molecular weight polyethylene material, it comprises following component by weight:
It is characterized in that, described method comprises:
1) mineral filler is dispersed in dispersion medium, then adds properties-correcting agent and coupling agent, disperse and be dried;
2) by supramolecule weight northylen, Low Density Polyethylene, carbon nanotube, in step 1) in the mineral filler and the oxidation inhibitor that obtain mix;
3) will be in step 2) in the mixture extruding pelletization that obtains, thereby obtain described modified ultra-high molecular weight polyethylene material.
9. the purposes in 3D prints according to the modified ultra-high molecular weight polyethylene material of any one in claim 1-6.
10. a 3D Method of printing, is characterized in that using according to the modified ultra-high molecular weight polyethylene material of any one in claim 1-6.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356618A (en) * | 2014-10-29 | 2015-02-18 | 衢州学院 | Biomass wood-plastic composite material for 3D (three-dimensional) printing and preparation method for biomass wood-plastic composite material |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1937763A2 (en) * | 2005-08-08 | 2008-07-02 | Cabot Corporation | Polymeric compositions containing nanotubes |
| WO2010035851A1 (en) * | 2008-09-24 | 2010-04-01 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Resin composition |
| US20110040007A1 (en) * | 2009-08-17 | 2011-02-17 | Laird Technologies, Inc. | Highly thermally-conductive moldable thermoplastic composites and compositions |
| EP2448383A1 (en) * | 2010-10-26 | 2012-05-02 | Politecnico di Torino | Process for producing conductive and/or piezoresistive traces on a polymeric substrate |
| CN102438798A (en) * | 2009-04-08 | 2012-05-02 | 纳米技术股份有限公司 | Continuous method assisted by ultrasound with a variable amplitude and frequency for the preparation of nanocompoundds based on polymers and nanoparticles |
-
2014
- 2014-04-30 CN CN201410183492.2A patent/CN103980595B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1937763A2 (en) * | 2005-08-08 | 2008-07-02 | Cabot Corporation | Polymeric compositions containing nanotubes |
| WO2010035851A1 (en) * | 2008-09-24 | 2010-04-01 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Resin composition |
| CN102438798A (en) * | 2009-04-08 | 2012-05-02 | 纳米技术股份有限公司 | Continuous method assisted by ultrasound with a variable amplitude and frequency for the preparation of nanocompoundds based on polymers and nanoparticles |
| US20110040007A1 (en) * | 2009-08-17 | 2011-02-17 | Laird Technologies, Inc. | Highly thermally-conductive moldable thermoplastic composites and compositions |
| EP2448383A1 (en) * | 2010-10-26 | 2012-05-02 | Politecnico di Torino | Process for producing conductive and/or piezoresistive traces on a polymeric substrate |
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| CN105622803A (en) * | 2014-11-17 | 2016-06-01 | 中国科学院化学研究所 | Novel purpose of random hyperbranched polyethylene |
| CN105622803B (en) * | 2014-11-17 | 2018-08-24 | 中国科学院化学研究所 | A kind of new application of random hyperbranched polyethylene |
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| CN113423558A (en) * | 2019-02-20 | 2021-09-21 | 巴塞尔聚烯烃股份有限公司 | Extrusion additive manufacturing process for producing polyethylene articles |
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| JPWO2022038941A1 (en) * | 2020-08-18 | 2022-02-24 | ||
| CN115867608A (en) * | 2020-08-18 | 2023-03-28 | 三井化学株式会社 | Ethylene polymer composition and use thereof |
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