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CN104031316A - Ultra-low density polypropylene composite material capable of being used for 3D printing and preparation method thereof. - Google Patents

Ultra-low density polypropylene composite material capable of being used for 3D printing and preparation method thereof. Download PDF

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Publication number
CN104031316A
CN104031316A CN201410256360.8A CN201410256360A CN104031316A CN 104031316 A CN104031316 A CN 104031316A CN 201410256360 A CN201410256360 A CN 201410256360A CN 104031316 A CN104031316 A CN 104031316A
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China
Prior art keywords
low density
composite material
polypropylene composite
extremely
prints
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Inventor
刘志
马璐
宋航
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Wenzhou Ke Lisu Industry Co Ltd
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Wenzhou Ke Lisu Industry Co Ltd
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Priority to CN201410256360.8A priority Critical patent/CN104031316A/en
Publication of CN104031316A publication Critical patent/CN104031316A/en
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—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
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • 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
    • B29C48/02—Small extruding apparatus, e.g. handheld, toy or laboratory 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
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • 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
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • 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
    • 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
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • 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
    • B29C2948/92895—Barrel or housing
    • 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
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams
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    • 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
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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Clinical Laboratory Science (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to an ultra-low density polypropylene composite material capable of being used for 3D printing and a preparation method thereof. The polypropylene composite material comprises the following composition in percentage by weight: 45-98% of polypropylene, 0-20% of a toughening agent, 0-20% of an inorganic filler, 1-10% of expandable microspheres, 0.2-0.5% of a nucleating agent, 0.2-2% of a stabilizing agent and 0-5% of other additives. The preparation method comprises the steps of weighing the raw materials according the percentage by weight, putting the materials into a high-speed mixer and carrying out dry-blending for 3-15 minutes, adding the mixed raw materials into a twin-screw extruder, carrying out melt extrusion, cooling and granulating, wherein the temperature of a first zone, a second zone, a third zone and a fourth zone in the screw cylinder are all 170-190 DEG C, the temperature of the machine head is 170-190 DEG C and the rotation speed of the twin-screw extruder is 100-1000 revolutions per minute. The ultra-low density polypropylene composite material disclosed by the invention has the advantages of low shrinkage, no warping, ultra low density, high rigidity and high toughness and can also be well suitable for 3D printing.

Description

A kind of extremely-low density polypropylene composite material that can be used for 3D printing and preparation method thereof
Technical field
The present invention relates to polypropylene composite material field, be specifically related to the extremely-low density polypropylene composite material that a kind of 3D of can be used for prints, and the preparation method of this matrix material.
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 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.
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, when 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.
Foam material is one of most important method realizing at present high-performance low density material, expended microsphere is a kind of unconventional pneumatogen, the shell being formed by thermoplastic resin and the whipping agent of Nei Bao form, thermoplastic resin enclosure uses 1 conventionally, 1-Ethylene Dichloride based copolymer, acrylic copolymer, acrylic copolymer, the whipping agent including mainly uses the hydro carbons such as Trimethylmethane or iso-pentane, and its boiling point is below the softening temperature of resin enclosure.After heating, microballoon can expand 40 times～100 times, after subcooling, can solidify.Due to its stable foaming character, lower commercial cost, has been widely applied to every field, and along with the continuous improvement of product, housing heat resisting temperature improves constantly, and has occurred heat-resisting 170 DEG C of above housings, has possessed and has been applied to polyacrylic potentiality.
Provide a kind of extremely-low density, good toughness, moulding fast can be used for the polypropylene composite material that 3D prints, have great importance for the development that promotes 3D printed material.
Summary of the invention
The object of the present invention is to provide polypropylene composite material that a kind of 3D of can be used for prints and preparation method thereof, this polypropylene composite material has advantages of that extremely-low density, good toughness, moulding are fast, has overcome existing 3D printed material limitation.
Object of the present invention can be achieved through the following technical solutions:
Can be used for the extremely-low density polypropylene composite material that 3D prints, formed by the raw material of following weight percent:
Wherein, described polypropylene is homo-polypropylene, block copolymerization propylene or the random copolymerization propylene of melt flow rate (MFR) (230 DEG C × 2.16kg) between 0.5-60g/10min, the comonomer of its co-polypropylene is common is ethene, and its content is within the scope of 1-15%.Preferred melt flow rate (MFR) (230 DEG C × 2.16kg) 3-40g/10min's, ethylene content is at the block copolymerization propylene of 4-10% scope.
Described toughner is any suitable POE (POE), and melt flow rate (MFR) (230 DEG C × 2.16kg) is 0.5-50g/10min.
Described mineral filler is one or more the composition in talcum powder, calcium carbonate, barium sulfate, and its median size is 1-20 μ m; Preferably median size is the talcum powder of 1-10 μ m.
Described expended microsphere is diameter 5～50 μ m, heat-resisting more than 170 DEG C, preferably diameter 5～20 μ m, heat-resisting 190 DEG C of above expended microspheres.Optional expended microsphere includes but not limited to F-190D, F230D, the F260D of Japanese Matsumoto Yushi-Seiyaku Co., Ltd., Expancel 093DU120, the 909DU80 of Akzo Nobel company of Sweden, 920DU40,920DU80,920DU120,930DU120,950DU80 etc.
Described nucleator is any suitable beta nucleater, includes but not limited to rare earth nucleator, the TMB-5 of Shanxi chemical institute etc. of Guangdong Wei Linna.
Described stablizer comprises primary antioxidant and auxiliary antioxidant, wherein primary antioxidant is hindered phenol or sulphur ester antioxidant, (chemical name is 1 to include but not limited to 3114,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl)-1,3,5-triazine-2,4,6[1H, 3H, 5H] triketone), one or more composition in 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); Auxiliary antioxidant is phosphorite kind antioxidant, include but not limited to one or both combinations in 618 (chemical name is distearyl pentaerythritol diphosphite), 168 (chemical name is tricresyl phosphite (2,4-di-tert-butyl) ester).
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 polypropylene composite material that can be used for 3D printing described above, its step is as follows:
1) take by weight ratio raw material;
2) polypropylene taking, toughner, mineral filler, expended microsphere, nucleator, stablizer and other additive are dry mixed to 3-15 minute in super mixer, mixed raw material is added in twin screw extruder to cooling granulation after melt extruding;
Wherein in barrel, temperature is: a district 170-190 DEG C, and two district 170-190 DEG C, three district 170-190 DEG C, four district 170-190 DEG C, head 170-190 DEG C, twin screw extruder rotating speed is 100-1000 rev/min.
Beneficial effect of the present invention is:
1, use the toughner of POE as polypropylene processing, can improve toughness, the reduction material contracts rate of material; Use beta nucleater to accelerate crystallization velocity, improved shaping speed, 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), reduce shrinking percentage; Adopt the mineral fillers such as superslide stone flour, significantly reduce shrinking percentage and improve simultaneously the rigidity of material; Expended microsphere can significantly reduce density of material in the performance that reduces by a small margin material, in the time printing, further foams, and has compensated the contraction of material.There is good over-all properties.
2, adopt all from main spout feeding manner, strengthened shearing, improved the dispersion effect of toughner, talcum powder, expended microsphere etc., further improved the performance of matrix material.
Embodiment
Be explained in detail below in conjunction with multiple embodiment of the present invention, thereby so that advantages and features of the invention can be easier to be those skilled in the art will recognize that, protection scope of the present invention made to more defining of clear and definite.
Embodiment 1
Take by weight percentage polypropylene 96.3%, F-230D and be 3%, TMB-5 is 0.2%, Irganox 1010 is 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, the material respectively weighing up is put into super mixer and be dry mixed 5 minutes, add again and in twin screw extruder, melt extrude granulation, wherein in barrel, temperature is: 180 DEG C, a district, two 185 DEG C, districts, three 185 DEG C, districts, four 190 DEG C, districts, head temperature is 180 DEG C, twin screw extruder rotating speed is made as to 500 revs/min, particle injection molding sample preparation on injection moulding machine after drying.
Embodiment 2
Take by weight percentage polypropylene 86.3%, talcum powder 10%, F-230D is 3%, TMB-5 is 0.2%, Irganox 1010 is 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, the material respectively weighing up is put into super mixer and be dry mixed 5 minutes, add again and in twin screw extruder, melt extrude granulation, wherein in barrel, temperature is: 180 DEG C, a district, two 185 DEG C, districts, three 185 DEG C, districts, four 190 DEG C, districts, head temperature is 180 DEG C, twin screw extruder rotating speed is made as to 500 revs/min, particle injection molding sample preparation on injection moulding machine after drying.
Embodiment 3
Take by weight percentage polypropylene 76.3%, talcum powder 20%, F-230D is 3%, TMB-5 is 0.2%, Irganox 1010 is 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, the material respectively weighing up is put into super mixer and be dry mixed 5 minutes, add again and in twin screw extruder, melt extrude granulation, wherein in barrel, temperature is: 180 DEG C, a district, two 185 DEG C, districts, three 185 DEG C, districts, four 190 DEG C, districts, head temperature is 180 DEG C, twin screw extruder rotating speed is made as to 500 revs/min, particle injection molding sample preparation on injection moulding machine after drying.
Embodiment 4
Take by weight percentage polypropylene 66.3%, POE 8180 is 10%, talcum powder 20%, F-230D is 3%, TMB-5 is 0.2%, Irganox 1010 is 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, the material respectively weighing up is put into super mixer and be dry mixed 5 minutes, add again and in twin screw extruder, melt extrude granulation, wherein in barrel, temperature is: 180 DEG C, a district, two 185 DEG C, districts, three 185 DEG C, districts, four 190 DEG C, districts, head temperature is 180 DEG C, twin screw extruder rotating speed is made as 500 revs/min, particle injection molding sample preparation on injection moulding machine after drying.
Embodiment 5
Take by weight percentage polypropylene 56.3%, POE 8180 is 20%, talcum powder 20%, F-230D is 3%, TMB-5 is 0.2%, Irganox 1010 is 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, the material respectively weighing up is put into super mixer and be dry mixed 5 minutes, add again and in twin screw extruder, melt extrude granulation, wherein in barrel, temperature is: 180 DEG C, a district, two 185 DEG C, districts, three 185 DEG C, districts, four 190 DEG C, districts, head temperature is 180 DEG C, twin screw extruder rotating speed is made as 500 revs/min, particle injection molding sample preparation on injection moulding machine after drying.
Embodiment 6
Take by weight percentage polypropylene 58.3%, POE 8180 is 20%, talcum powder 20%, F-230D is 1%, TMB-5 is 0.2%, Irganox 1010 is 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, the material respectively weighing up is put into super mixer and be dry mixed 5 minutes, add again and in twin screw extruder, melt extrude granulation, wherein in barrel, temperature is: 180 DEG C, a district, two 185 DEG C, districts, three 185 DEG C, districts, four 190 DEG C, districts, head temperature is 180 DEG C, twin screw extruder rotating speed is made as 500 revs/min, particle injection molding sample preparation on injection moulding machine after drying.
Embodiment 7
Take by weight percentage polypropylene 49.3%, POE 8180 is 20%, talcum powder 20%, F-230D is 10%, TMB-5 is 0.2%, Irganox 1010 is 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, the material respectively weighing up is put into super mixer and be dry mixed 5 minutes, add again and in twin screw extruder, melt extrude granulation, wherein in barrel, temperature is: 180 DEG C, a district, two 185 DEG C, districts, three 185 DEG C, districts, four 190 DEG C, districts, head temperature is 180 DEG C, twin screw extruder rotating speed is made as 500 revs/min, particle injection molding sample preparation on injection moulding machine after drying.
Comparative example 1
Take by weight percentage polypropylene 99.5%, Irganox 1010 and be 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, the material respectively weighing up is put into super mixer and be dry mixed 5 minutes, add again and in twin screw extruder, melt extrude granulation, wherein in barrel, temperature is: 180 DEG C, a district, two 185 DEG C, districts, three 185 DEG C, districts, four 190 DEG C, districts, head temperature is 180 DEG C, twin screw extruder rotating speed is made as 500 revs/min, particle injection molding sample preparation on injection moulding machine after drying.
Performance evaluation mode:
Sample rate test is undertaken by ISO 1183A standard, the g/cm of unit 3; Bending property test is undertaken by ISO 178 standards, 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 ISO 179 standards, and specimen size is 80 × 10 × 4mm, and notch depth is 2mm, unit K j/m 2; Material contracts rate is tested according to ISO 2577, the % of unit.
Each embodiment and comparative example formula and the performance test results are shown in following each table:
Table 1 embodiment 1-7 and comparative example 1 material prescription (% by weight)
Table 2 embodiment 1-7 and comparative example 1 the performance test results
Can find out from the contrast of comparative example 1 and embodiment 1-7, toughner and talcum powder all can significantly reduce material contracts rate, rigidity, toughness have also obtained significantly improving simultaneously, and expended microsphere makes significantly to reduce in rigidity, a small amount of situation about reducing of toughness the density of material.Embodiment 5 excellent combination properties, mechanical property and ABS approach, and have significantly reduced density of material simultaneously.Each embodiment is extruded into 3mm lines, and prints for FDM, do not need to use hott bed, all printable go out not good, the good toughness of warpage, precision, there is the product of extremely-low density simultaneously.
Note: in the composite-material formula of embodiment and comparative example, polypropylene used is the block copolymerization propylene of melt flow rate (MFR) (230 DEG C × 2.16kg) 3-40g/10min, ethylene content 4-10%.
Toughening agent is the ethylene-octene copolymer POE 8180 of DOW company.
Mineral filler used is the talcum powder of the sheet structure of median size 1-10 μ m.
Used can foam microspheres be the expended microsphere of heat-resisting 230 DEG C, the F-230D of Japanese Matsumoto Yushi-Seiyaku Co., Ltd..
Nucleator used is beta nucleater, is the TMB-5 of Shanxi chemical institute.
Stablizer used be ICE company of Britain Negonox DSTP (chemical name be thio-2 acid stearic alcohol ester), (chemical name is four [β-(3 to the Irganox 1010 of Ciba company, 5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester) and the Igrafos168 (chemical name is tricresyl phosphite (2,4-di-tert-butyl) ester) of Ciba company.
Other additive used is that those skilled in the art think one or more composition in required tinting material, processing aid, lubricant.

Claims (10)

1. can be used for the extremely-low density polypropylene composite material that 3D prints, formed by the raw material of following weight percent:
2. a kind of extremely-low density polypropylene composite material that 3D prints that can be used for according to claim 1, it is characterized in that: under the test condition of 230 DEG C × 2.16kg, described polypropylene is homo-polypropylene, block copolymerization propylene or the random copolymerization propylene of melt flow rate (MFR) (230 DEG C × 2.16kg) between 0.5-60g/10min, wherein the comonomer of co-polypropylene is common is ethene, and its content is within the scope of 1-15%.
3. a kind of extremely-low density polypropylene composite material that 3D prints that can be used for according to claim 1, is characterized in that: described toughner is ethylene-octene copolymer (POE).
4. a kind of extremely-low density polypropylene composite material that 3D prints that can be used for according to claim 3, is characterized in that: described toughner POE elastomerics, under the test condition of 230 DEG C × 2.16kg, melt flow rate (MFR) is 0.5-50g/10min.
5. a kind of extremely-low density 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 combinations in talcum powder, calcium carbonate and barium sulfate, and its median size is 1-20 μ m.
6. a kind of extremely-low density polypropylene composite material that 3D prints that can be used for according to claim 1, is characterized in that: described expended microsphere diameter 5～50 μ m are heat-resisting more than 170 DEG C.
7. a kind of extremely-low density 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 extremely-low density polypropylene composite material that 3D prints that can be used for according to claim 1, it is characterized in that: described stablizer comprises primary antioxidant and auxiliary antioxidant, primary antioxidant is Hinered phenols or sulphur ester antioxidant, and auxiliary antioxidant is phosphorite kind antioxidant.
9. according to claim 8ly can be used for the extremely-low density polypropylene composite material that 3D prints, it is characterized in that: described primary antioxidant is 3114,1010, one or more combinations in DSTP; Described auxiliary antioxidant is one or both combinations in 618 and 168, and other described additive comprises that those skilled in the art think one or more composition in required tinting material, processing aid and lubricant.
10. a method of preparing the extremely-low density polypropylene composite material of the 3D of can be used for printing claimed in claim 1, is characterized in that, the method comprises the following steps: 1) take by weight ratio raw material; 2) polypropylene, toughner, mineral filler, expended microsphere, 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 170-190 DEG C, and two district 170-190 DEG C, three district 170-190 DEG C, four district 170-190 DEG C, head 170-190 DEG C, twin screw extruder rotating speed is 100-1000 rev/min.
CN201410256360.8A 2014-06-09 2014-06-09 Ultra-low density polypropylene composite material capable of being used for 3D printing and preparation method thereof. Pending CN104031316A (en)

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