CN103739954B - A kind of can be used for PP composite material of 3D printing and preparation method thereof - Google Patents

A kind of can be used for PP composite material of 3D printing and preparation method thereof Download PDF

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CN103739954B
CN103739954B CN201310738303.9A CN201310738303A CN103739954B CN 103739954 B CN103739954 B CN 103739954B CN 201310738303 A CN201310738303 A CN 201310738303A CN 103739954 B CN103739954 B CN 103739954B
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composite material
printing
antioxidant
toughener
polypropylene
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CN103739954A (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
Chongqing Pret New Materials Co Ltd
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Shanghai Pret Composites Co Ltd
Zhejiang Pret New Materials Co Ltd
Chongqing Pret New Materials Co Ltd
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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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • 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
    • B29C48/04—Particle-shaped
    • 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
    • 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
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means 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
    • B29C48/40—Means 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
    • 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
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/875—Thermal 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
    • 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
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • 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
    • 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
    • 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
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear
    • 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
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • 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
    • C08L2205/24—Crystallisation aids
    • C08L2205/242—Beta spherulite nucleating agents
    • 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
    • C08L2207/10—Peculiar tacticity
    • C08L2207/14—Amorphous or atactic polypropylene

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  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a kind of can be used for PP composite material of 3D printing and preparation method thereof, it is made up of the raw material of following weight percents：Polypropylene 70 98%, transparent toughener 1 20%, inorganic filler 0 10%, nucleator 0.1 0.5%, stabilizer 0.2 2%, other additives 0 5%. it is an advantage of the invention that：1st, the toughener for using a kind of propylene-based elastomeric to process as polypropylene, can improve the toughness of material, reduce Material shrinkage rate, while excessively not affecting transparency；Accelerate crystallization rate using beta nucleater, shaping speed is improve, spherulite size has been refined, transparency is improve, while crystal area density is reduced, reduce shrinkage factor；Using ultrapure superfine talcum powder or high mesh number calcium sulfate crystal whiskers etc., reduce shrinkage factor while keeping preferable transparency.With good combination property.2nd, using all from main spout feeding manner, shearing is strengthened, the dispersion effect of toughener, talcum powder etc. is improve, further increase the performance of composite.

Description

A kind of can be used for PP composite material of 3D printing and preparation method thereof
Technical field
The present invention relates to a kind of PP composite material, specially a kind of PP composite material that can be used for 3D printing, And the preparation method of this composite, belong to polymer modification and manufacture field.
Background technology
Rapid shaping technique is also referred to as 3D printing technique, is born in the later stage eighties 20th century, be based on material stacking method A kind of high-new manufacturing technology.It is a revolutionary technology for overturning classical production process, the steam engine that is described as continuing, computer and mutually The great invention of another item after networking.It collects mechanical engineering, CAD, reverse Engineering Technology, Layered Manufacturing Technology, Numeric Control Technology, material Material science, it can automatically, directly, quickly and accurately by design philosophy be changed into the prototype with certain function or Part is directly manufactured, so as to provide a kind of high efficiency, low cost for aspects such as part prototype, the verifications of new design philosophy Realization rate.
One important branch of 3D printing, is the personal printing that rose from 2008 or so.Most of individual 3D beats Print machine completes printing shaping using FDM (Deformation In The Fdm Process Fused Deposition Modeling).Substantially the original of the technology Reason be by thermal plastic high polymer long filament（The current a diameter of 1.75mm and 3mm of the coupling of the printer of main flow）It is sent to using gear Macromolecule is melted by high temperature hot junction and continuously extrusion melts macromolecule, and is built by way of successively piling up under being accurately positioned Three-dimensional body.
Modal 3D printing macromolecule has ABS and PLA in the market（PLA）Two kinds.ABS mechanical property is good, especially Which is that toughness is high, is also widely used in the other 3D printing of technical grade；The gas for having " unpleasant " when having the disadvantage to print, melting is produced Raw, be not suitable for the environment such as office, operating room, and opaque.The advantage of PLA be transparent, melting when nothing unpleasant peculiar smell, Degradable；Shortcoming is poor heat resistance, poor mechanical property, especially easily brittle fracture occurs, significantly limit printing object Use.
Polypropylene has good processing characteristics and physics, a chemical property, extremely low density, and the valency of relative moderate Lattice, and be widely used, it is the most fast general-purpose thermoplastic plastic of current growth rate.But polypropylene toughness is mostly poor, shrink Rate is big, and crystallization rate is slow, is easily shunk using product during 3D printing and is deformed partially crisp etc. defect of warpage, product.
There is provided that a kind of density is low, heat resistance is good, transparency is high, intensity good, shrinkage factor is low, the 3D that can be used for of good toughness beats The PP composite material of print, has great importance for the development for promoting 3D printing material.
Content of the invention
It is an object of the invention to a kind of low-density of exploitation, high rigidity, high tenacity, the high grade of transparency can be used for 3D printing PP composite material, to overcome 3D printing material limitation.
Another object of the present invention is to provide for the preparation method of this PP composite material.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of PP composite material that can be used for 3D printing, is made up of the raw material of following weight percents：
Wherein,
Described polypropylene is melt flow rate (MFR)（230℃×2.16kg）Homopolymerization third between 0.5-60g/10min Alkene or random copolymerization propylene, the comonomer of wherein random copolymerization propylene are common for ethene, and its content is in the range of 1-7%.It is preferred that Melt flow rate (MFR)（230℃×2.16kg）The random copolymerization propylene of 3-40g/10min.
Any suitable propylene-alpha olefin copolymer of described transparent toughener, including but not limited to exxonmobil company Vistamaxx series 6102,6202 etc..
The inorganic filler is one or more the composition in ultrapure superfine talcum powder, calcium sulfate crystal whiskers etc., and which is put down All particle diameter is 1-20 μm；It is preferred that talcum powder of the average grain diameter for 1-10 μm.
The nucleator is any suitable beta nucleater, including but not limited to the rare earth nucleator of Guangdong Wei Linna, Shanxi TMB-5 of chemical institute etc..
The stabilizer includes primary antioxidant and auxiliary antioxidant, and wherein primary antioxidant is hindered phenol or thioesters class antioxygen Agent, including but not limited to 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 be four [β-（3,5- di-t-butyl 4- hydroxy phenyls）Propionic acid] pentaerythrite Ester）、DSTP（Chemical name is thio-2 acid tristearin alcohol ester）In one or more composition；Auxiliary antioxidant is Phosphorite kind antioxidant, including but not limited to 618（Chemical name is distearyl pentaerythritol diphosphite）、 168（Chemical name is phosphorous acid three (2,4- di-tert-butyl) ester）In one or two combination.
Other additives described include those skilled in the art think needed for colouring agent, processing aid, in lubricant One or more composition.
The preparation method of the above-mentioned modified polypropylene composite material that can be used for 3D printing, its step are as follows：
1) raw material is weighed by weight ratio；
2) by polypropylene, transparent toughener, inorganic filler, nucleator, stabilizer and other additives in super mixer In dry-mixed 3-15 minute, by mixed raw material add double screw extruder in, cooling granulation after melt extruding；Wherein barrel Interior temperature is：One 180-220 DEG C of area, two 180-220 DEG C of areas, three 180-220 DEG C of areas, four 180-220 DEG C of areas, head 180-220 DEG C, double screw extruder rotating speed is 100-1000 rev/min.
It is an advantage of the invention that：
1st, the toughener for using a kind of propylene-based elastomeric to process as polypropylene, can improve toughness, the reduction of material Material shrinkage rate, while excessively do not affect transparency；Accelerate crystallization rate using beta nucleater, shaping speed is improve, refinement Spherulite size, improves transparency, while reducing crystal area density（Common PP crystallization primarily forms alpha-crystal, density 0.936g/ cm3, beta nucleater promote alpha-crystal be converted into β crystal, density 0.922g/cm3）, reduce shrinkage factor；Using ultrapure extra fine talc Powder or high mesh number calcium sulfate crystal whiskers etc., reduce shrinkage factor while keeping preferable transparency.With good combination property.
2nd, using all from main spout feeding manner, shearing is strengthened, improves the dispersion effect of toughener, talcum powder etc. Really, the performance of composite is further increased.
Specific embodiment
The present invention is described in further detail with reference to embodiment.The scope of the present invention is carried in detail in the claims Go out, be not restricted by the embodiments.
In the composite-material formula of embodiment and comparative example, polypropylene used is melt flow rate (MFR)（230℃× 2.16kg）The random copolymerization propylene of 3-40g/10min, ethylene contents 1-7%.
Transparent toughener used is propylene-alpha olefin copolymer, the 6102 of the vistamaxx series of exxonmobil.
Inorganic filler used is the ultrapure talcum powder of the laminated structure of average grain diameter 1-10 μm.
Nucleator used is beta nucleater, is the TMB-5 of Shanxi chemical institute.
Stabilizer used is the Negonox DSTP of ICE company of Britain（Chemical name is thio-2 acid tristearin alcohol ester）、 The Irganox1010 of Ciba company（Chemical name be four [β-（3,5- di-t-butyl 4- hydroxy phenyls）Propionic acid] pentaerythrite Ester）, and Ciba company Igrafos168（Chemical name is phosphorous acid three (2,4- di-tert-butyl) ester）.
In colouring agent of other additives used for needed for those skilled in the art think, processing aid, lubricant one The composition of kind or more.
Embodiment 1
Weigh by weight percentage polypropylene 89.3%, 6102 for 10%, TMB-5 be 0.2%, Irganox1010 be 0.1%, It is 0.3% that Igrafos168 is 0.1%, Negonox DSTP, dry-mixed 5 minutes in super mixer, adds twin-screw extrusion Melt extrude granulation in machine, wherein temperature is in barrel：One 180 DEG C of area, two 205 DEG C of areas, three 220 DEG C of areas, four 210 DEG C of areas, machine 210 DEG C, double screw extruder rotating speed is 500 revs/min.Particle injection moulding sample preparation on injection (mo(u)lding) machine after drying.
Embodiment 2
Weigh by weight percentage polypropylene 84.3%, 6102 for 10%, ultrapure talcum powder 5%, TMB-5 be 0.2%, It is 0.3% for 0.1%, Negonox DSTP that Irganox1010 is 0.1%, Igrafos168, dry-mixed 5 points in super mixer Clock, adds in double screw extruder and melt extrudes granulation, and wherein in barrel, temperature is：One 180 DEG C of area, two 205 DEG C of areas, 3rd area 220 DEG C, four 210 DEG C of areas, 210 DEG C of head, double screw extruder rotating speed are 500 revs/min.Particle is after drying in injection (mo(u)lding) machine Upper injection moulding sample preparation.
Embodiment 3
Weigh by weight percentage polypropylene 79.3%, 6102 for 10%, ultrapure talcum powder 10%, TMB-5 be 0.2%, It is 0.3% for 0.1%, Negonox DSTP that Irganox1010 is 0.1%, Igrafos168, dry-mixed 5 points in super mixer Clock, adds in double screw extruder and melt extrudes granulation, and wherein in barrel, temperature is：One 180 DEG C of area, two 205 DEG C of areas, 3rd area 220 DEG C, four 210 DEG C of areas, 210 DEG C of head, double screw extruder rotating speed are 500 revs/min.Particle is after drying in injection (mo(u)lding) machine Upper injection moulding sample preparation.
Embodiment 4
Weigh by weight percentage polypropylene 84.3%, 6102 for 5%, ultrapure talcum powder 10%, TMB-5 be 0.2%, It is 0.3% for 0.1%, Negonox DSTP that Irganox1010 is 0.1%, Igrafos168, dry-mixed 5 points in super mixer Clock, adds in double screw extruder and melt extrudes granulation, and wherein in barrel, temperature is：One 180 DEG C of area, two 205 DEG C of areas, 3rd area 220 DEG C, four 210 DEG C of areas, 210 DEG C of head, double screw extruder rotating speed are 500 revs/min.Particle is after drying in injection (mo(u)lding) machine Upper injection moulding sample preparation.
Embodiment 5
Weigh by weight percentage polypropylene 69.3%, 6102 for 20%, ultrapure talcum powder 10%, TMB-5 be 0.2%, It is 0.3% for 0.1%, Negonox DSTP that Irganox1010 is 0.1%, Igrafos168, dry-mixed 5 points in super mixer Clock, adds in double screw extruder and melt extrudes granulation, and wherein in barrel, temperature is：One 180 DEG C of area, two 205 DEG C of areas, 3rd area 220 DEG C, four 210 DEG C of areas, 210 DEG C of head, double screw extruder rotating speed are 500 revs/min.Particle is after drying in injection (mo(u)lding) machine Upper injection moulding sample preparation.
Comparative example 1
Weigh by weight percentage polypropylene 99.5%, Irganox1010 for 0.1%, Igrafos168 be 0.1%, Negonox DSTP is 0.3%, dry-mixed 5 minutes in super mixer, adds in double screw extruder and melt extrudes granulation, Wherein in barrel, temperature is：One 180 DEG C of area, two 205 DEG C of areas, three 220 DEG C of areas, four 210 DEG C of areas, 210 DEG C of head, twin-screw extrusion Machine rotating speed is 500 revs/min.Particle injection moulding sample preparation on injection (mo(u)lding) machine after drying.
Performance evaluation mode：
Sample rate test is carried out by ISO1183A standard, unit g/cm3；The test of sample tensile property is marked by ISO527-2 Standard is carried out, and specimen size is 170 × 10 × 4mm, and draw speed is 50mm/min, units MPa；Bending property is tested by ISO178 Standard is carried out, and specimen size is 80 × 10 × 4mm, span 64mm, rate of bending 2mm/min, units MPa；Charpy Impact Can test is carried out by ISO179 standard, and specimen size is 80 × 10 × 4mm, and notch depth is 2mm, unit K j/m2；Thermal deformation temperature Degree is carried out according to ISO75-2 standard, batten size 80*10*4, load 0.45MPa, 120 DEG C/Hr of programming rate, unit DEG C；Mist Degree is tested according to ASTMD-1003, thickness 1mm, unit %.Material shrinkage rate is tested according to ISO2577, unit %.
Each embodiment and comparative example formula and the performance test results see below Lie Gebiao：
1 embodiment 1-5 of table and 1 material prescription of comparative example (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 toughener - 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
2 embodiment 1-5 of table and 1 the performance test results of comparative example
Typical PLA Typical 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
Bending modulus 1700 2600 1154 963 1330 1590 1705 1410
Notch impact strength 3.0 20 6.1 24.3 22.4 21.3 9.1 41.3
Heat distortion temperature 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 shrinkage rate 0.65 0.60 1.05 0.84 0.73 0.65 0.70 0.59
Beta nucleater be can be seen that from the contrast of comparative example 1 and embodiment 1-5 and considerably reduce PP composite material Mist degree.And transparent toughener and talcum powder all can slightly improve the mist degree of composite, but Material shrinkage rate can be greatly reduced, While rigidity, toughness, heat resistance have also obtained significantly improving, 3 excellent combination property of embodiment, mechanical property are connect with ABS Closely, preferable transparency is maintained.Each embodiment is extruded into 3mm lines, and is printed for FDM, it is not necessary to using heat Bed, all can print out not warpage, precision good, relatively transparent while product with excellent rigid toughness and heat resistance.

Claims (8)

1. a kind of PP composite material that can be used for 3D printing, it is characterised in that：It is made up of the raw material of following weight percents：
The nucleator is beta nucleater；Described polypropylene is poly- for homopolymerization of the melt flow rate (MFR) between 0.5-60g/10min The comonomer of propylene or atactic copolymerized polypropene, wherein atactic copolymerized polypropene is ethene, and its content is in the range of 1-7%.
2. a kind of PP composite material that can be used for 3D printing according to claim 1, it is characterised in that：Described is poly- Propylene for melt flow rate (MFR) for 3-40g/10min atactic copolymerized polypropene.
3. a kind of PP composite material that can be used for 3D printing according to claim 1, it is characterised in that：Described is saturating Bright toughener is propylene-alpha olefin copolymer.
4. a kind of PP composite material that can be used for 3D printing according to claim 1, it is characterised in that：Described inorganic Filler is one or more the composition in ultrapure superfine talcum powder and calcium sulfate crystal whiskers, and its average grain diameter is 1-20 μ m.
5. a kind of PP composite material that can be used for 3D printing according to claim 4, it is characterised in that：Described inorganic Filler is 1-10 μm of talcum powder for average grain diameter.
6. a kind of PP composite material that can be used for 3D printing according to claim 1, it is characterised in that：Described stable Agent includes primary antioxidant and auxiliary antioxidant, and wherein primary antioxidant is hindered phenol or sulphur ester antioxidant；Auxiliary antioxidant is Asia Phosphate or esters antioxidant.
7. a kind of PP composite material that can be used for 3D printing according to claim 6, it is characterised in that：Described master Antioxidant includes one or more the composition in 3114,1010 and DSTP；Auxiliary antioxidant includes but is not limited to 618 With one or two combinations in 168.
8. a kind of method for preparing the PP composite material that can be used for 3D printing described in claim 1, it is characterised in that：Its step Rapid as follows：
1) raw material is weighed by weight ratio；
2) polypropylene, transparent toughener, inorganic filler, nucleator, stabilizer and other additives are done in super mixer Mixed 3-15 minute, mixed raw material is added in double screw extruder, cooling granulation after melt extruding；Wherein barrel interior temperature Spend and be：One 180-220 DEG C of area, two 180-220 DEG C of areas, three 180-220 DEG C of areas, four 180-220 DEG C of areas, 180-220 DEG C of head, double Screw extruder rotating speed is 100-1000 rev/min.
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