CN103739954A - Polypropylene composite material for 3D (Three Dimensional) printing and preparation method thereof - Google Patents

Polypropylene composite material for 3D (Three Dimensional) printing and preparation method thereof Download PDF

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Publication number
CN103739954A
CN103739954A CN201310738303.9A CN201310738303A CN103739954A CN 103739954 A CN103739954 A CN 103739954A CN 201310738303 A CN201310738303 A CN 201310738303A CN 103739954 A CN103739954 A CN 103739954A
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polypropylene
polypropylene composite
prints
antioxidant
composite
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CN103739954B (en
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陈勇
张鹰
张祥福
周文
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Shanghai Pret Composites Co Ltd
Zhejiang Pret New Materials Co Ltd
Chongqng Pret New Materials Co Ltd
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Shanghai Pret Composites Co Ltd
Zhejiang Pret New Materials Co Ltd
Chongqng Pret New Materials Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/14Copolymers of propene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion 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
    • B29C48/04Particle-shaped
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/78Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/875Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/9258Velocity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/9258Velocity
    • B29C2948/9259Angular velocity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885Screw or gear
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895Barrel or housing
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/24Crystallisation aids
    • C08L2205/242Beta spherulite nucleating agents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/10Peculiar tacticity
    • C08L2207/14Amorphous or atactic polypropylene

Abstract

The invention discloses a polypropylene composite material for 3D (Three Dimensional) printing and a preparation method thereof. The polypropylene composite material is composed of following raw materials in percentage by weight: 70%-98% of polypropylene, 1%-20% of a transparent toughening agent, 0-10% of inorganic fillers, 0.1%-0.5% of a nucleating agent, 0.2%-2% of a stabilizing agent and 0-5% of other additives. The polypropylene composite material has the advantages that 1 a propylene-based elastic body is used as the toughening agent for processing polypropylene so that the roughness of materials can be improved and the shrinkage rate of the materials is reduced; the transparency is not greatly influenced; a beta nucleating agent is used for accelerating a crystallization speed; the molding speed is improved, the size of a spherical crystal is thinned and the transparency is improved; the density of a crystal region is reduced and the shrinkage rate is reduced; super-pure and superfine talcum powder or calcium sulfate crystal whiskers with a high mesh number and the like are adopted so that the shrinkage rate is reduced and the good transparency is kept. The polypropylene composite material for the 3D printing has the advantages that 1 the comprehensive performance is good; 2 a manner of wholly feeding from a main feeding opening is adopted so that the dispersion effects of the toughening agent, the talcum powder and the like are improved, and the performance of the composite material is further improved.

Description

A kind of polypropylene composite material that can be used for 3D printing and preparation method thereof
Technical field
The present invention relates to a kind of polypropylene composite material, be specially the polypropylene composite material that a kind of 3D of can be used for prints, and the preparation method of this matrix material, polymer modification and manufacture field belonged to.
Background technology
Rapid shaping technique also claims 3D printing technique, is born in the later stage eighties 20th century, is the high-new manufacturing technology of one based on material stacking method.It is a revolutionary technology of overturning classical production process, is described as another great invention behind steamer, computer and internet.It integrates mechanical engineering, CAD, reverse Engineering Technology, layering manufacturing technology, Numeric Control Technology, Materials science, it can change design philosophy into automatically, directly, quickly and accurately and has the prototype of certain function or direct finished parts, thereby provides a kind of means that realize of high efficiency, low cost for aspects such as the verifications of part prototype, new design philosophy.
The important branch that 3D prints is that the individual of rising from about 2008 prints.Most individual 3D printers uses FDM (Deformation In The Fdm Process Fused Deposition Modeling) to complete printing shaping.The ultimate principle of this technology is to utilize gear be sent to high temperature hot junction by polymer melting and extrude continuously melting polymer thermal plastic high polymer long filament (the coupling diameter of the printer of main flow is 1.75mm and 3mm at present), and accurately under location, by the mode of successively piling up, is building three-dimensional body.
Modal 3D prints polymer in the market two kinds of ABS and poly(lactic acid) (PLA).ABS mechanical property is good, and especially toughness is high, is also widely used in other 3D of technical grade and prints; Shortcoming has the γ-ray emission of " unpleasant " while being printing, melting, be not suitable for the environment such as office, working spaces, and opaque.That the advantage of poly(lactic acid) is is transparent, during melting without unpleasant peculiar smell, degradable; Shortcoming is poor heat resistance, and brittle rupture especially easily occurs poor mechanical property, has limited greatly the use of printing object.
Polypropylene has good processing characteristics and physics, chemical property, extremely low density, and relatively cheap price, and be widely used, be the fastest general-purpose thermoplastic plastic of current rate of growth.But polypropylene toughness is mostly poor, and shrinking percentage is large, and crystallization velocity is slow, while adopting 3D to print, product easily shrinks and produces the defects such as distortion warpage, product are partially crisp.
Provide that a kind of density is low, resistance toheat good, transparency is high, intensity is good, shrinking percentage is low, good toughness can be used for the polypropylene composite material that 3D prints, for the development that promotes 3D printed material, have great importance.
Summary of the invention
The object of the invention is to develop the polypropylene composite material that can be used for 3D printing of a kind of low density, high rigidity, high tenacity, high-clarity, to overcome 3D printed material limitation.
Another object of the present invention is the preparation method for this polypropylene composite material is provided.
Object of the present invention can be achieved through the following technical solutions:
Can be used for the polypropylene composite material that 3D prints, by the raw material of following weight percent, formed:
Wherein,
Described polypropylene is homo-polypropylene or the random copolymerization propylene of melt flow rate (MFR) (230 ℃ × 2.16kg) between 0.5-60g/10min, and wherein the comonomer of random copolymerization propylene is common is ethene, and its content is within the scope of 1-7%.The preferably random copolymerization propylene of melt flow rate (MFR) (230 ℃ × 2.16kg) 3-40g/10min.
Any suitable propylene-alpha olefin multipolymer of described transparent toughner, include but not limited to exxonmobil company vistamaxx series 6102,6202 etc.
Described mineral filler is one or more the composition in ultrapure superfine talcum powder, calcium sulfate crystal whiskers etc., and its median size is 1-20 μ m; Preferably median size is the talcum powder of 1-10 μ m.
Described nucleator is any suitable beta nucleater, includes but not limited to the rare earth nucleator of Guangdong Wei Linna, the TMB-5 of Shanxi chemical institute etc.
Described stablizer comprises primary antioxidant and auxiliary antioxidant, wherein primary antioxidant is hindered phenol or sulphur ester antioxidant, include but not limited to that 3114(chemical name is 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl)-1,3,5-triazine-2,4,6[1H, 3H, 5H] triketone), 1010(chemical name is four [β-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester), DSTP(chemical name is the stearic alcohol ester of thio-2 acid) in one or more composition; Auxiliary antioxidant is phosphorite kind antioxidant, include but not limited to that 618(chemical name is distearyl pentaerythritol diphosphite), 168(chemical name is tricresyl phosphite (2,4-di-tert-butyl) ester) in one or both combinations.
Described other additive comprises that those skilled in the art think one or more composition in required tinting material, processing aid, lubricant.
The preparation method of the above-mentioned modified polypropylene composite material that can be used for 3D printing, its step is as follows:
1) take by weight ratio raw material;
2) polypropylene, transparent toughner, mineral filler, nucleator, stablizer and other additive are dry mixed to 3-15 minute in super mixer, mixed raw material is added in twin screw extruder, cooling granulation after melt extruding; Wherein in barrel, temperature is: a district 180-220 ℃, and two district 180-220 ℃, three district 180-220 ℃, four district 180-220 ℃, head 180-220 ℃, twin screw extruder rotating speed is 100-1000 rev/min.
Advantage of the present invention is:
1, use the toughner of a kind of propylene-based elastomeric as polypropylene processing, can improve toughness, the reduction material contracts rate of material, exceed simultaneously and affect transparency; Use beta nucleater accelerate crystallization velocity, improved shaping speed, refinement spherulite size, improved transparency, reduced crystal area density (common PP crystallization mainly forms alpha-crystal, density 0.936g/cm simultaneously 3, beta nucleater promotes that alpha-crystal is converted into β crystal, density 0.922g/cm 3), reduced shrinking percentage; Adopt ultrapure superfine talcum powder or high order to count calcium sulfate crystal whiskers etc., reduce shrinking percentage and keep good transparency simultaneously.There is good over-all properties.
2, adopt all from main spout feeding manner, strengthened shearing, improved the dispersion effect of toughner, talcum powder etc., further improved the performance of matrix material.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.Scope of the present invention proposes in claims, is not subject to the restriction of these embodiment.
In the composite-material formula of embodiment and comparative example, polypropylene used is the random copolymerization propylene of melt flow rate (MFR) (230 ℃ × 2.16kg) 3-40g/10min, ethylene content 1-7%.
Transparent toughner used is propylene-alpha olefin multipolymer, 6102 of the vistamaxx series of exxonmobil.
Mineral filler used is the ultrapure talcum powder of the sheet structure of median size 1-10 μ m.
Nucleator used is beta nucleater, is the TMB-5 of Shanxi chemical institute.
Stablizer used is that the Negonox DSTP(chemical name of Britain ICE company is the stearic alcohol ester of thio-2 acid), the Irganox1010(chemical name of Ciba company is four [β-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester) and the Igrafos168(chemical name of Ciba company be tricresyl phosphite (2,4-di-tert-butyl) ester).
Other additive used is that those skilled in the art think one or more composition in required tinting material, processing aid, lubricant.
Embodiment 1
Take by weight percentage polypropylene 89.3%, 6102 and be 10%, TMB-5 is 0.2%, Irganox1010 is 0.1%, Igrafos168 is 0.1%, Negonox DSTP is 0.3%, in super mixer, be dry mixed 5 minutes, add again and in twin screw extruder, melt extrude granulation, wherein in barrel, temperature is: 180 ℃, a district, two 205 ℃, districts, three 220 ℃, districts, four 210 ℃, districts, 210 ℃ of heads, twin screw extruder rotating speed is 500 revs/min.Particle injection molding sample preparation on injection moulding machine after drying.
Embodiment 2
Take by weight percentage polypropylene 84.3%, 6102 and be 10%, ultrapure talcum powder 5%, TMB-5 are 0.2%, Irganox1010 is 0.1%, Igrafos168 is 0.1%, Negonox DSTP is 0.3%, in super mixer, be dry mixed 5 minutes, add again and in twin screw extruder, melt extrude granulation, wherein in barrel, temperature is: 180 ℃, a district, two 205 ℃, districts, three 220 ℃, districts, four 210 ℃, districts, 210 ℃ of heads, twin screw extruder rotating speed is 500 revs/min.Particle injection molding sample preparation on injection moulding machine after drying.
Embodiment 3
Take by weight percentage polypropylene 79.3%, 6102 and be 10%, ultrapure talcum powder 10%, TMB-5 are 0.2%, Irganox1010 is 0.1%, Igrafos168 is 0.1%, Negonox DSTP is 0.3%, in super mixer, be dry mixed 5 minutes, add again and in twin screw extruder, melt extrude granulation, wherein in barrel, temperature is: 180 ℃, a district, two 205 ℃, districts, three 220 ℃, districts, four 210 ℃, districts, 210 ℃ of heads, twin screw extruder rotating speed is 500 revs/min.Particle injection molding sample preparation on injection moulding machine after drying.
Embodiment 4
Take by weight percentage polypropylene 84.3%, 6102 and be 5%, ultrapure talcum powder 10%, TMB-5 are 0.2%, Irganox1010 is 0.1%, Igrafos168 is 0.1%, Negonox DSTP is 0.3%, in super mixer, be dry mixed 5 minutes, add again and in twin screw extruder, melt extrude granulation, wherein in barrel, temperature is: 180 ℃, a district, two 205 ℃, districts, three 220 ℃, districts, four 210 ℃, districts, 210 ℃ of heads, twin screw extruder rotating speed is 500 revs/min.Particle injection molding sample preparation on injection moulding machine after drying.
Embodiment 5
Take by weight percentage polypropylene 69.3%, 6102 and be 20%, ultrapure talcum powder 10%, TMB-5 are 0.2%, Irganox1010 is 0.1%, Igrafos168 is 0.1%, Negonox DSTP is 0.3%, in super mixer, be dry mixed 5 minutes, add again and in twin screw extruder, melt extrude granulation, wherein in barrel, temperature is: 180 ℃, a district, two 205 ℃, districts, three 220 ℃, districts, four 210 ℃, districts, 210 ℃ of heads, twin screw extruder rotating speed is 500 revs/min.Particle injection molding sample preparation on injection moulding machine after drying.
Comparative example 1
Take by weight percentage polypropylene 99.5%, Irganox1010 and be 0.1%, Igrafos168 is 0.1%, Negonox DSTP is 0.3%, in super mixer, be dry mixed 5 minutes, add again and in twin screw extruder, melt extrude granulation, wherein in barrel, temperature is: 180 ℃, a district, two 205 ℃, districts, three 220 ℃, districts, four 210 ℃, districts, 210 ℃ of heads, twin screw extruder rotating speed is 500 revs/min.Particle injection molding sample preparation on injection moulding machine after drying.
Performance evaluation mode:
Sample rate test is undertaken by ISO1183A standard, the g/cm of unit 3; The test of sample tensile property is undertaken by ISO527-2 standard, and specimen size is 170 × 10 × 4mm, and draw speed is 50mm/min, units MPa; Bending property test is undertaken by ISO178 standard, and specimen size is 80 × 10 × 4mm, span 64mm, rate of bending 2mm/min, units MPa; The test of simply supported beam impact property is undertaken by ISO179 standard, and specimen size is 80 × 10 × 4mm, and notch depth is 2mm, unit K j/m 2; Heat-drawn wire is carried out according to ISO75-2 standard, batten size 80*10*4, load 0.45MPa, 120 ℃/Hr of heat-up rate, unit ℃; Mist degree is tested according to ASTMD-1003, thickness 1mm, the % of unit.Material contracts rate is tested according to ISO2577, the % of unit.
Each embodiment and comparative example formula and the performance test results are shown in following each table:
Table 1 embodiment 1-5 and comparative example 1 material prescription (% by weight)
? Comparative example 1 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Polypropylene 99.5 89.3 84.3 79.3 84.3 69.3
Transparent toughner - 10 10 10 5 20
Talcum powder - - 5 10 10 10
Beta nucleater - 0.2 0.2 0.2 0.2 0.2
1010 0.1 0.1 0.1 0.1 0.1 0.1
168 0.1 0.1 0.1 0.1 0.1 0.1
DSTP 0.3 0.3 0.3 0.3 0.3 0.3
Table 2 embodiment 1-5 and comparative example 1 the performance test results
? Typical case PLA Typical case ABS Comparative example 1 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Density 1.24 1.04 0.896 0.884 0.932 0.959 0.963 0.954
Tensile strength 40 46 25 22.6 23.0 23.3 24.9 20.7
Modulus in flexure 1700 2600 1154 963 1330 1590 1705 1410
Notched Izod impact strength 3.0 20 6.1 24.3 22.4 21.3 9.1 41.3
Heat-drawn wire 40 85 88.3 79.4 94.8 104.2 109.5 96.4
Mist degree 10 Opaque 24 11 16 23 22 24
Material contracts rate 0.65 0.60 1.05 0.84 0.73 0.65 0.70 0.59
From the contrast of comparative example 1 and embodiment 1-5, can find out, beta nucleater has significantly reduced the mist degree of polypropylene composite material.And transparent toughner and talcum powder all can slightly improve the mist degree of matrix material, but can significantly reduce material contracts rate, rigidity, toughness, thermotolerance have also obtained significantly improving simultaneously, embodiment 3 excellent combination properties, mechanical property and ABS approach, and have kept good transparency simultaneously.Each embodiment is extruded into 3mm lines, and prints for FDM, do not need to use hott bed, all printable go out not warpage, precision good, more transparent, there is excellent rigidity toughness and stable on heating product simultaneously.

Claims (10)

1. can be used for the polypropylene composite material that 3D prints, it is characterized in that: the raw material by following weight percent forms:
2. a kind of polypropylene composite material that 3D prints that can be used for according to claim 1, it is characterized in that: described polypropylene is homo-polypropylene or the random copolymerization propylene of melt flow rate (MFR) between 0.5-60g/10min, wherein the comonomer of random copolymerization propylene is ethene, and its content is within the scope of 1-7%.
3. a kind of polypropylene composite material that 3D prints that can be used for according to claim 2, is characterized in that: described polypropylene is that melt flow rate (MFR) is the random copolymerization propylene of 3-40g/10min.
4. a kind of polypropylene composite material that 3D prints that can be used for according to claim 1, is characterized in that: described transparent toughner is propylene-alpha olefin multipolymer.
5. a kind of polypropylene composite material that 3D prints that can be used for according to claim 1, is characterized in that: described mineral filler is one or more the composition in ultrapure superfine talcum powder and calcium sulfate crystal whiskers, and its median size is 1-20 μ m.
6. a kind of polypropylene composite material that 3D prints that can be used for according to claim 5, is characterized in that: described mineral filler is that median size is the talcum powder of 1-10 μ m.
7. a kind of polypropylene composite material that 3D prints that can be used for according to claim 1, is characterized in that: described nucleator is beta nucleater.
8. a kind of polypropylene composite material that 3D prints that can be used for according to claim 1, is characterized in that: described stablizer comprises primary antioxidant and auxiliary antioxidant, and wherein primary antioxidant is hindered phenol or sulphur ester antioxidant; Auxiliary antioxidant is phosphorite kind antioxidant.
9. a kind of polypropylene composite material that 3D prints that can be used for according to claim 8, is characterized in that: described primary antioxidant include but not limited to 3114,1010 and DSTP in one or more composition; Auxiliary antioxidant includes but not limited to one or both combinations in 618 and 168.
10. the preparation method who can be used for the modified polypropylene composite material of 3D printing described in claim 1, is characterized in that: its step is as follows:
1) take by weight ratio raw material;
2) polypropylene, transparent toughner, mineral filler, nucleator, stablizer and other additive are dry mixed to 3-15 minute in super mixer, mixed raw material is added in twin screw extruder, cooling granulation after melt extruding; Wherein in barrel, temperature is: a district 180-220 ℃, and two district 180-220 ℃, three district 180-220 ℃, four district 180-220 ℃, head 180-220 ℃, twin screw extruder rotating speed is 100-1000 rev/min.
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