CN107936358A - A kind of 3D printing expanded material and preparation method thereof - Google Patents

A kind of 3D printing expanded material and preparation method thereof Download PDF

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Publication number
CN107936358A
CN107936358A CN201711233892.XA CN201711233892A CN107936358A CN 107936358 A CN107936358 A CN 107936358A CN 201711233892 A CN201711233892 A CN 201711233892A CN 107936358 A CN107936358 A CN 107936358A
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parts
printing
expanded material
weight
ethylene
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Chinese (zh)
Inventor
覃晓捷
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Guangxi Jing Kang Trade & Trade Co Ltd
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Guangxi Jing Kang Trade & Trade Co Ltd
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Priority to CN201711233892.XA priority Critical patent/CN107936358A/en
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    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y50/00—Data acquisition or data processing for additive manufacturing
    • B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0042—Use of organic additives containing silicon
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/5406—Silicon-containing compounds containing elements other than oxygen or nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/48—Wearing apparel
    • B29L2031/50—Footwear, e.g. shoes or parts thereof
    • B29L2031/504—Soles
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate

Abstract

The present invention provides a kind of 3D printing expanded material and preparation method thereof, belongs to expanded material technical field.The expanded material is made of the raw material of following parts by weight：80 100 parts of ethylene-vinyl acetate copolymer, 15 25 parts of ethylene octene copolymer, 45 55 parts of precipitated calcium carbonate, 58 parts of anti-wear agent, 6 10 parts of foaming agent, 46 parts of γ-chloropropyl triethoxysilane, 69 parts of naphthenic oil, 35 parts of blowing promotor, 12 parts of antioxidant；The foaming agent is to azodicarbonamide.The present invention is prepared using can be used for 3D printing sport footwear, has preferable wearability, elasticity, and hardness is moderate.

Description

A kind of 3D printing expanded material and preparation method thereof
【Technical field】
The present invention relates to 3D printing field of material technology, and in particular to a kind of 3D printing expanded material and preparation method thereof.
【Background technology】
3D printing is also known as rapid shaping technique, also referred to as increases material manufacturing technology, is that conventional tool, fixture is not required in one kind And lathe, but based on digital model file, the material for having adhesion using metal dust or plastics etc. successively prints To manufacture the technology of arbitrary shape article.The article that 3D printer can manufacture is very much, such as aircraft, pistol, food, human body for another example Organ, toy for children etc..3D printing technique is an important breakthrough of world's manufacturing technology field over the past two decades.
3D printing at present mainly includes fused glass pellet (Fused Deposition Modeling, FDM), selectivity Laser sintering and moulding (Selective Laser Sintering, SLS), Stereolithography (stereo lithography Apparatus, SLA), laminated solid body shaping (Laminated Object Manufacturing, LOM) etc. technology, wherein FDM It is with fastest developing speed, using most.FDM refers to that Filamentous thermoplastic is sent into nozzle by wire feeder, is heated to melt in the showerhead State, is extruded through nozzle.The filamentary material of molten state is extruded out, and the path controlled according to the individual-layer data of three-dimensional software extrudes And solidified in specified position coagulation forming, layer by layer deposition, eventually form whole three-dimensional objects.The operating environment of FDM is clean, peace Entirely, technique is simple, easily operated, and does not produce rubbish, therefore has widened operation occasion significantly.Its raw materials is with spool silk Form provide, be easily portable and quick-replaceable.
At present, in terms of 3D printing technique has applied to the making of sport footwear, the efficiency of production can be not only greatly improved, It can also be made according to the foot amount body of each user, there is a good market prospects, but due to the hysteresis of 3D printing investigation of materials, The optional material of in the market is limited, and the sole that existing printed material is come out by 3D printing is in wearability, soft or hard comfort It need to be improved in terms of Deng additional function.
【The content of the invention】
The goal of the invention of the present invention is：For above-mentioned problem, there is provided a kind of 3D printing expanded material and its system Preparation Method, the present invention are prepared using can be used for 3D printing sport footwear, have preferable wearability, elasticity, and hardness It is moderate.
To achieve these goals, the technical solution adopted by the present invention is as follows：
A kind of 3D printing expanded material, is made of the raw material of following parts by weight：Ethylene-vinyl acetate copolymer 80- 100 parts, 15-25 parts of ethylene-octene copolymer, 45-55 parts of precipitated calcium carbonate, 5-8 parts of anti-wear agent, 6-10 parts of foaming agent, γ-chlorine 4-6 parts of propyl-triethoxysilicane, 6-9 parts of naphthenic oil, 3-5 parts of blowing promotor, 1-2 parts of antioxidant.
Preferably, the content of vinyl acetate is 20% in ethylene-vinyl acetate copolymer；Foaming agent is to azo diformazan acyl Amine；The blowing promotor is by 3-5 parts of cassava whole-powders, 6-9 parts of acetylation mono-fatty acid glycerides, 1-2 portions of seaweed by weight Sour sodium sulfuric ester composition.
Preferably, the anti-wear agent is prepared by following methods：Mixer is warming up to 330-350 DEG C, then in 20-30 weights Measure and 3-8 parts by weight carbonyl iron, 6-9 parts by weight abrasion resistant carbon black and 2-4 parts of silane coupling agents added in the ptfe micropowder of part, Mixer is put into after mixing, after the speed mixing 20-30min of 150-200r/min, 12-20h is placed, then in compression molding Vulcanize 10-20min in the condition that temperature is 170-185 DEG C, pressure is 10-20MPa on machine, obtain anti-wear agent.
Preferably, antioxidant 2,6- toluene di-tert-butyl phenols or thio lauric anhydride.
The preparation method of above-mentioned 3D printing expanded material, comprises the following steps：
(1) all raw materials are got out by weight；
(2) foaming agent is mixed with blowing promotor, adding a certain amount of water makes foaming agent and blowing promotor complete wetting, adopts 20-35min is stirred under the rotating speed of 100-200r/min with mixer, the powder that particle diameter is 20-50 mesh then is made with comminutor Grain, obtains foaming raw material A；
(3) by ethylene-vinyl acetate copolymer, ethylene-octene copolymer, precipitated calcium carbonate in high-speed mixer with The rotating speed mixing of 1000-1200r/min 10-15 minutes, then adds naphthenic oil, γ-chloropropyl triethoxysilane, anti-oxidant Agent, anti-wear agent add foaming raw material A with rotating speed mixing 10-15 minutes of 300-400r/min after then heating to 80-95 DEG C, Extruded after mixing in double screw extruder, temperature is between 120 DEG C -200 DEG C in control double screw extruder, rotating speed 200- 600r/min, and be granulated by pelleter；Then wire drawing is extruded by single screw extrusion machine, gained wire drawing is 3D printing foaming Material, available for 3D printing foamed shoe sole.
For the 3D printing expanded material in printing, it is 190-220 DEG C to control melting temperature, keeps 10- at this temperature The nozzle through printer sprays after 20min, after the completion of printing, foaming 20-30min after being placed in 200 ± 2 DEG C of constant temperature oven Afterwards, natural cooling is taken out up to the product to be printed.
In conclusion by adopting the above-described technical solution, the beneficial effects of the invention are as follows：
1st, used in the present invention to azodicarbonamide as ethylene-vinyl acetate copolymer and ethylene-octene copolymer Foaming agent, due to the influence of the factors such as electrostatic, easily reunite to azodicarbonamide, thus influence its in the polymer point Property is dissipated, causes to foam uneven, influences the intensity and heat-insulating property of material, by adding by cassava whole-powder, acetylation list glycerine Fatty acid ester, sodium alginate sulfuric ester composition blowing promotor and hybrid fine particles are made, be then added to mixed foaming in polymer, Material surface skinning can be made smooth, distribution of cells is uniform in material, cell size is homogeneous, forms closed pore hard structure；This hair It is bright that coupling agent is also done using γ-chloropropyl triethoxysilane, by being chemically reacted between high molecular polymer, improve Interface interaction between each material, the bonding strength between reinforced resin；Acted on by the mutual cooperation between above-mentioned each raw material, Gained expanded material can be made to obtain preferable hardness, be adapted to the sole for making sport footwear.
2nd, special anti-wear agent is used in the present invention, by ptfe micropowder, carbonyl iron, abrasion resistant carbon black and silane coupled Agent is mixed, and sole tool can be made to have good wearability, avoid the mill of sole on the premise of elastic comfort level is not influenced Damage.
【Embodiment】
In order to more clearly express the present invention, below by way of specific embodiment, the invention will be further described.Following reality Apply in example, the content of vinyl acetate is 20% in ethylene-vinyl acetate copolymer.
Embodiment 1
A kind of 3D printing expanded material, is made of the raw material of following parts by weight：Ethylene-vinyl acetate copolymer 80 Part, 15 parts of ethylene-octene copolymer, 45 parts of precipitated calcium carbonate, 5 parts of anti-wear agent, foaming agent is to 6 parts of azodicarbonamide, γ-chlorine 4 parts of propyl-triethoxysilicane, 6 parts of naphthenic oil, 3 parts of blowing promotor, 2,6- 1 part of toluene di-tert-butyl phenols；Wherein, foaming helps Agent is made of 3 parts of cassava whole-powders, 6 parts of acetylation mono-fatty acid glycerides, 1 part of sodium alginate sulfuric ester by weight.
Anti-wear agent is prepared by following methods：Mixer is warming up to 330 DEG C, it is then micro- in the polytetrafluoroethylene (PTFE) of 20 parts by weight 3 parts by weight carbonyl irons, 6 parts by weight abrasion resistant carbon blacks and 2 parts of vinyl silanes are added in powder, mixer are put into after mixing, with 150r/ After the speed mixing 20min of min, 12h is placed, then in the bar that temperature is 170 DEG C, pressure is 20MPa on vulcanizing press Part vulcanizes 10min, obtains anti-wear agent.
The preparation method of above-mentioned 3D printing expanded material, comprises the following steps：
(1) all raw materials are got out by weight；
(2) foaming agent is mixed with blowing promotor, adding a certain amount of water makes foaming agent and blowing promotor complete wetting, adopts 35min is stirred under the rotating speed of 100r/min with mixer, the powder that particle diameter is 20-50 mesh then is made with comminutor, must send out Steep raw material A；
(3) by ethylene-vinyl acetate copolymer, ethylene-octene copolymer, precipitated calcium carbonate in high-speed mixer with The rotating speed of 1000r/min mixes 15 minutes, then adds naphthenic oil, γ-chloropropyl triethoxysilane, antioxidant, wear-resisting Agent is mixed 15 minutes with the rotating speed of 300r/min, foaming raw material A is added after then heating to 80 DEG C, in twin-screw extrusion after mixing Extruded in machine, temperature is between 120 DEG C -200 DEG C in control double screw extruder, and temperature is set as successively：One area 120-130 DEG C, two 135-145 DEG C of areas, three 150-160 DEG C of areas, four 160-170 DEG C of areas, five 170-180 DEG C of areas, six 180-190 DEG C of areas, 7th area 195-200 DEG C, eight 190-195 DEG C of areas, nine 190-195 DEG C of areas, ten 185-190 DEG C of areas, 180-190 DEG C of head temperature, rotating speed is 200r/min, and be granulated by pelleter；Then wire drawing is extruded by single screw extrusion machine, gained wire drawing is 3D printing foaming Material.
Embodiment 2
A kind of 3D printing expanded material, is made of the raw material of following parts by weight：Ethylene-vinyl acetate copolymer 90 Part, 20 parts of ethylene-octene copolymer, 50 parts of precipitated calcium carbonate, 6 parts of anti-wear agent, foaming agent is to 8 parts of azodicarbonamide, γ-chlorine 5 parts of propyl-triethoxysilicane, 7 parts of naphthenic oil, 4 parts of blowing promotor, 2,6- 1 part of toluene di-tert-butyl phenols；Blowing promotor is pressed Parts by weight are made of 4 parts of cassava whole-powders, 7 parts of acetylation mono-fatty acid glycerides, 1.5 parts of sodium alginate sulfuric esters.
Anti-wear agent is prepared by following methods：Mixer is warming up to 340 DEG C, it is then micro- in the polytetrafluoroethylene (PTFE) of 25 parts by weight 5 parts by weight carbonyl irons, 8 parts by weight abrasion resistant carbon blacks and 3 parts of vinyl silanes are added in powder, mixer are put into after mixing, with 180r/ After the speed mixing 25min of min, 18h is placed, then in the bar that temperature is 180 DEG C, pressure is 15MPa on vulcanizing press Part vulcanizes 15min, obtains anti-wear agent.
The preparation method of above-mentioned 3D printing expanded material, comprises the following steps：
(1) all raw materials are got out by weight；
(2) foaming agent is mixed with blowing promotor, adding a certain amount of water makes foaming agent and blowing promotor complete wetting, adopts 30min is stirred under the rotating speed of 150r/min with mixer, the powder that particle diameter is 20-50 mesh then is made with comminutor, must send out Steep raw material A；
(3) by ethylene-vinyl acetate copolymer, ethylene-octene copolymer, precipitated calcium carbonate in high-speed mixer with The rotating speed of 1100r/min mixes 12 minutes, then adds naphthenic oil, γ-chloropropyl triethoxysilane, antioxidant, wear-resisting Agent is mixed 12 minutes with the rotating speed of 350r/min, the foaming raw material A is added after then heating to 90 DEG C, in twin-screw after mixing Extruded in extruder, temperature is between 120 DEG C -200 DEG C in control double screw extruder, and temperature is set as successively：One area 120-130 DEG C, two 135-145 DEG C of areas, three 150-160 DEG C of areas, four 160-170 DEG C of areas, five 170-180 DEG C of areas, six area 180-190 DEG C, seven 195-200 DEG C of areas, eight 190-195 DEG C of areas, nine 190-195 DEG C of areas, ten 185-190 DEG C of areas, 180-190 DEG C of head temperature, Rotating speed is 400r/min, and is granulated by pelleter；Then wire drawing is extruded by single screw extrusion machine, gained wire drawing is that 3D is beaten Print and distribute foam material.
Embodiment 3
A kind of 3D printing expanded material, is made of the raw material of following parts by weight：Ethylene-vinyl acetate copolymer 100 Part, 25 parts of ethylene-octene copolymer, 55 parts of precipitated calcium carbonate, 8 parts of anti-wear agent, foaming agent to 10 parts of azodicarbonamide, γ- 6 parts of chloropropyl triethoxysilane, 9 parts of naphthenic oil, 5 parts of blowing promotor, thio 2 parts of lauric anhydride；Wherein blowing promotor is by weight Amount part is made of 5 parts of cassava whole-powders, 9 parts of acetylation mono-fatty acid glycerides, 2 parts of sodium alginate sulfuric esters.
Anti-wear agent is prepared by following methods：Mixer is warming up to 350 DEG C, it is then micro- in the polytetrafluoroethylene (PTFE) of 30 parts by weight 8 parts by weight carbonyl irons, 9 parts by weight abrasion resistant carbon blacks and 4 parts of vinyl silanes are added in powder, mixer are put into after mixing, with 200r/ After the speed mixing 30min of min, 20h is placed, then in the bar that temperature is 185 DEG C, pressure is 20MPa on vulcanizing press Part vulcanizes 20min, obtains anti-wear agent.
The preparation method of above-mentioned 3D printing expanded material, comprises the following steps：
(1) all raw materials are got out by weight；
(2) foaming agent is mixed with blowing promotor, adding a certain amount of water makes foaming agent and blowing promotor complete wetting, adopts 20min is stirred under the rotating speed of 200r/min with mixer, the powder that particle diameter is 20-50 mesh then is made with comminutor, must send out Steep raw material A；
(3) by ethylene-vinyl acetate copolymer, ethylene-octene copolymer, precipitated calcium carbonate in high-speed mixer with The rotating speed of 1200r/min mixes 10 minutes, then adds naphthenic oil, γ-chloropropyl triethoxysilane, antioxidant, wear-resisting Agent is mixed 10 minutes with the rotating speed of 400r/min, foaming raw material A is added after then heating to 95 DEG C, in twin-screw extrusion after mixing Extruded in machine, temperature is between 120 DEG C -200 DEG C in control double screw extruder, and temperature is set as successively：One area 120-130 DEG C, two 135-145 DEG C of areas, three 150-160 DEG C of areas, four 160-170 DEG C of areas, five 170-180 DEG C of areas, six 180-190 DEG C of areas, 7th area 195-200 DEG C, eight 190-195 DEG C of areas, nine 190-195 DEG C of areas, ten 185-190 DEG C of areas, 180-190 DEG C of head temperature, rotating speed is 600r/min, and be granulated by pelleter；Then wire drawing is extruded by single screw extrusion machine, gained wire drawing is 3D printing foaming Material.
Comparative example 1
The difference of this comparative example and embodiment 2 is, is not added with blowing promotor.
Comparative example 2
The difference of this comparative example and embodiment 2 is that anti-wear agent is containing only abrasion resistant carbon black.
Comparative example 3
The difference of this comparative example and embodiment 2 is that ethylene-octene copolymer is copolymerized using ethene-vinyl acetate Thing replaces.
Gained 3D printing expanded material is prepared to above-described embodiment 1-3 and comparative example 1-3, is printed using 3D printer After sole, wearability, apparent and abscess situation are tested, and using GB/T1681-1991 standard testings impact rebound degree, are adopted With GB/T531.1-2008 standard testing Shore C hardness.It the results are shown in Table 1.Control device melting temperature is 200 when wherein printing DEG C, the nozzle through printer sprays after keeping 15min at this temperature, after the completion of printing, is placed in 200 ± 2 DEG C of constant temperature oven In after foaming 20-30min after, take out natural cooling up to the product to be printed.
1 the performance test results of table
Rebound degree/% Hardness Abrasion index Abscess, surface smoothness
Embodiment 1 51 44 283 Abscess dense uniform, surfacing
Embodiment 2 52 44 288 Abscess dense uniform, surfacing
Embodiment 3 51 43 283 Abscess dense uniform, surfacing
Comparative example 1 39 54 218 The loose uneven, surface irregularity of abscess
Comparative example 2 47 42 179 Abscess dense uniform, surfacing
Comparative example 3 44 38 256 Abscess dense uniform, surfacing
As can be seen from the above table, the expanded material that prepared by embodiment 1-3 has preferable foaming effect, and material abscess is fine and close Homogeneous, surfacing is smooth, and elasticity and hardness are moderate, from barasion coefficient as can be seen that its wear-resisting property is more preferable.In comparative example 1 Due to being not added with blowing promotor, cell diameter heterogeneity and abscess is loose, material surface is not smooth enough, makes its elasticity bad, material Matter is partially hard；Comparative example 2 is since anti-wear agent uses abrasion resistant carbon black, and dosage addition is insufficient, and wearability is not good enough；Comparative example 3 by It is modified in being not added with ethylene-octene copolymer so that material is excessively soft.

Claims (6)

1. a kind of 3D printing expanded material, it is characterised in that mainly made of the raw material of following parts by weight：Ethyl vinyl acetate second 80-100 parts of alkene copolymer, 15-25 parts of ethylene-octene copolymer, 45-55 parts of precipitated calcium carbonate, 5-8 parts of anti-wear agent, foaming agent 6-10 parts, γ -4-6 parts of chloropropyl triethoxysilane, 6-9 parts of naphthenic oil, 3-5 parts of blowing promotor, 1-2 parts of antioxidant；Institute It is to azodicarbonamide to state foaming agent.
2. 3D printing expanded material according to claim 1, it is characterised in that：The blowing promotor is by 3- by weight 5 parts of cassava whole-powders, 6-9 parts of acetylation mono-fatty acid glycerides, 1-2 parts of sodium alginate sulfuric ester compositions.
3. 3D printing expanded material according to claim 1, it is characterised in that：The anti-wear agent is prepared by following methods： Mixer is warming up to 330-350 DEG C, 3-8 parts by weight carbonyls are then added in the ptfe micropowder of 20-30 parts by weight Iron, 2-3 parts by weight abrasion resistant carbon black and 6-9 parts of silane coupling agents, mixer is put into after mixing, close with the speed of 150-200r/min Refine 20-30min after, place 12-20h, then on vulcanizing press temperature be 170-185 DEG C, pressure be 10-20MPa's Condition vulcanizes 10-20min, obtains anti-wear agent.
4. 3D printing expanded material according to claim 1, it is characterised in that：Acetic acid in ethylene-vinyl acetate copolymer The content of ethene is 20%.
5. 3D printing expanded material according to claim 1, it is characterised in that：Antioxidant is 2,6- di-t-butyls to first Phenol or thio lauric anhydride.
6. the preparation method of the 3D printing expanded material according to any one of claim 1-5, it is characterised in that including with Lower step：
(1) all raw materials are got out by weight；
(2) foaming agent is mixed with blowing promotor, adding a certain amount of water makes foaming agent and blowing promotor complete wetting, using stirring Mix machine and 20-35min is stirred under the rotating speed of 100-200r/min, the powder that particle diameter is 20-50 mesh then is made with comminutor, obtains Foaming raw material A；
(3) by ethylene-vinyl acetate copolymer, ethylene-octene copolymer, precipitated calcium carbonate in high-speed mixer with 1000- The rotating speed mixing of 1200r/min 10-15 minutes, then adds naphthenic oil, γ-chloropropyl triethoxysilane, antioxidant, resistance to Grinding agent adds foaming raw material A, after mixing with rotating speed mixing 10-15 minutes of 300-400r/min after then heating to 80-95 DEG C Extruded in double screw extruder, temperature is between 120 DEG C -200 DEG C in control double screw extruder, rotating speed 200-600r/ Min, and be granulated by pelleter；Then wire drawing is extruded by single screw extrusion machine, gained wire drawing is 3D printing expanded material, Available for 3D printing foamed shoe sole.
CN201711233892.XA 2017-11-30 2017-11-30 A kind of 3D printing expanded material and preparation method thereof Withdrawn CN107936358A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110193931A (en) * 2019-06-10 2019-09-03 安踏（中国）有限公司 A kind of method of 3D printing high-performance foam midsole

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Publication number Priority date Publication date Assignee Title
CN103319776A (en) * 2013-07-01 2013-09-25 中国皮革和制鞋工业研究院 Functional gradient foamed sole material and preparation method thereof
CN104497453A (en) * 2014-11-26 2015-04-08 上海品科橡塑材料有限公司 New rubber wear-resisting agent and composition thereof
CN106220980A (en) * 2016-07-31 2016-12-14 谢新莉 A kind of compound article of footwear material and preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103319776A (en) * 2013-07-01 2013-09-25 中国皮革和制鞋工业研究院 Functional gradient foamed sole material and preparation method thereof
CN104497453A (en) * 2014-11-26 2015-04-08 上海品科橡塑材料有限公司 New rubber wear-resisting agent and composition thereof
CN106220980A (en) * 2016-07-31 2016-12-14 谢新莉 A kind of compound article of footwear material and preparation method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110193931A (en) * 2019-06-10 2019-09-03 安踏（中国）有限公司 A kind of method of 3D printing high-performance foam midsole

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Application publication date: 20180420