CN113004622A - Polypropylene powder for selective laser sintering 3D printing and preparation method thereof - Google Patents
Polypropylene powder for selective laser sintering 3D printing and preparation method thereof Download PDFInfo
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- CN113004622A CN113004622A CN202011527342.0A CN202011527342A CN113004622A CN 113004622 A CN113004622 A CN 113004622A CN 202011527342 A CN202011527342 A CN 202011527342A CN 113004622 A CN113004622 A CN 113004622A
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- -1 Polypropylene Polymers 0.000 title claims abstract description 189
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 187
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 187
- 239000000843 powder Substances 0.000 title claims abstract description 129
- 238000000110 selective laser sintering Methods 0.000 title claims abstract description 43
- 238000010146 3D printing Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 18
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 18
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002216 antistatic agent Substances 0.000 claims abstract description 17
- 239000002667 nucleating agent Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 55
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 32
- 229910052593 corundum Inorganic materials 0.000 claims description 32
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 32
- 239000002994 raw material Substances 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 25
- 239000006185 dispersion Substances 0.000 claims description 24
- 239000004611 light stabiliser Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 229920000289 Polyquaternium Polymers 0.000 claims description 15
- 238000012216 screening Methods 0.000 claims description 15
- BVXGBMBOZMRULW-UHFFFAOYSA-N 1-n,4-n-dicyclohexylbenzene-1,4-dicarboxamide Chemical compound C=1C=C(C(=O)NC2CCCCC2)C=CC=1C(=O)NC1CCCCC1 BVXGBMBOZMRULW-UHFFFAOYSA-N 0.000 claims description 13
- 238000009826 distribution Methods 0.000 claims description 13
- 230000008014 freezing Effects 0.000 claims description 13
- 238000007710 freezing Methods 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 102220042174 rs141655687 Human genes 0.000 claims description 13
- 102220076495 rs200649587 Human genes 0.000 claims description 13
- 102220043159 rs587780996 Human genes 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 12
- 239000007822 coupling agent Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 10
- 235000021355 Stearic acid Nutrition 0.000 claims description 9
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 9
- 239000008117 stearic acid Substances 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 239000012974 tin catalyst Substances 0.000 claims description 5
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- USYJXNNLQOTDLW-UHFFFAOYSA-L calcium;heptanedioate Chemical compound [Ca+2].[O-]C(=O)CCCCCC([O-])=O USYJXNNLQOTDLW-UHFFFAOYSA-L 0.000 claims description 2
- JILYTPDQRCHWPA-UHFFFAOYSA-L calcium;octanedioate Chemical compound [Ca+2].[O-]C(=O)CCCCCCC([O-])=O JILYTPDQRCHWPA-UHFFFAOYSA-L 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 238000013329 compounding Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 15
- 238000007639 printing Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 11
- 229920002554 vinyl polymer Polymers 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 238000007873 sieving Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000005245 sintering Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000007648 laser printing Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011089 mechanical engineering Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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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
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L53/005—Modified block copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to the field of 3D printing materials, in particular to polypropylene powder for selective laser sintering 3D printing and a preparation method thereof. Comprises the following components in parts by weight: 100 parts of polypropylene resin, 8-10 parts of maleic anhydride grafted POE, 3-5 parts of nucleating agent, 3-5 parts of weather-resistant agent, 3-5 parts of lubricant, 0.1-0.5 part of antistatic agent and 0.2-0.4 part of hydrophobic fumed silica. The polypropylene powder material prepared by the method has good fluidity, stable printing process, good size precision of sintered parts, high toughness and high impact strength.
Description
Technical Field
The invention relates to the field of 3D printing materials, in particular to polypropylene powder for selective laser sintering 3D printing and a preparation method thereof.
Background
The 3D printing (i.e., additive manufacturing) technology is an advanced manufacturing technology that builds rapid prototyping of an entity by adding materials in a layer-by-layer manufacturing manner based on a digital model file, relates to a plurality of aspects such as materials science, informatics, precision mechanical engineering, and has a very strong competitive power in modern manufacturing industry. In recent 20 years, 3D printing technology has developed very rapidly as a new rapid prototyping technology, and has very important chinese applications in the national economy and high technology fields of industrial manufacturing, aerospace, national defense and military, biomedical energy, and the like. The types include fused deposition techniques, selective laser sintering techniques, stereolithography techniques, and layered solid fabrication techniques.
The Selective Laser Sintering (SLS) technique is one of the most important processing techniques for 3D printing, and c.r. dechard et al in patent US4863538 first proposed the concept of selective laser sintering and successfully developed the laser sintering process in 1989. Simply speaking, the laser beam is selectively sintered under the control of a computer according to the information of the layered cross section, the next layer of sintering is carried out after one layer is finished, and redundant powder is removed after all the layers of sintering are finished, so that the sintered part can be obtained. The selective laser sintering technology has many advantages, such as wide powder material selection, wide applicability, simpler manufacturing process, high forming precision, no need of a supporting structure and capability of directly sintering parts, so that the selective laser sintering technology is more and more widely valued in modern manufacturing industry.
The types of molding materials used in SLS technology are wide, including polymers, paraffins, metals, ceramics, and composites thereof. Among materials that can be used for laser sintering, polymer materials are receiving much attention due to their excellent properties, but at present, polymer powder raw materials that can be directly applied to SLS technology and successfully produce molded products with small dimensional errors, regular surfaces and low porosity are few, and nylon is mainly used in the market, and accounts for about 95% of the whole SLS polymer powder, and there is an urgent need to develop more kinds of polymer powder materials.
The polypropylene has the advantages of small density, high strength, heat resistance, good insulating property, low price, excellent chemical stability and the like, is one of general plastics which are widely researched and applied at present, and also becomes one of research hotspots of SLS (selective laser sintering) technical application materials. However, polypropylene has the disadvantages of poor impact resistance, poor toughness, large molding shrinkage and the like, so that the problems of easy buckling deformation, poor size precision of a sintered part, high brittleness, low toughness, easy breakage and the like exist in the sintering process in the application of SLS technology. Therefore, how to prepare a high-performance polypropylene material suitable for selective laser sintering 3D printing becomes a research focus in this field.
Disclosure of Invention
The invention provides a preparation method of a polypropylene powder material suitable for selective laser sintering 3D printing.
A polypropylene powder for selective laser sintering 3D printing comprises the following components in parts by weight: 100 parts of polypropylene resin, 8-10 parts of maleic anhydride grafted POE, 3-5 parts of nucleating agent, 3-5 parts of weather-resistant agent, 3-5 parts of lubricant, 0.1-0.5 part of antistatic agent and 0.2-0.4 part of hydrophobic fumed silica.
In one embodiment, the polypropylene resin is cross-linked and condensed with tetramethyltetravinylcyclotetrasiloxane (D4 vi).
In one embodiment, the polypropylene powder is further loaded with thermally conductive particles.
In one embodiment, the thermally conductive particles are Al2O3。
In one embodiment, the nucleating agent is one of N, N' -dicyclohexylterephthalamide, calcium suberate, calcium pimelate.
In one embodiment, the weathering agent is an antioxidant and light stabilizer 1: 1, and (b) a compound system.
In one embodiment, the antioxidant is antioxidant 1010, antioxidant 168.
In one embodiment, the light stabilizers are light stabilizer 770, light stabilizer 328.
In one embodiment, the lubricant is one or a mixture of two of stearic acid, butyl stearate, PE wax, and silicone powder.
In one embodiment, the antistatic agent is a polyquaternium.
In one embodiment, the method for preparing the polypropylene resin comprises the following steps:
the preparation method of the polypropylene powder for selective laser sintering 3D printing comprises the following steps:
step 1, uniformly mixing polypropylene resin, maleic anhydride grafted POE, a nucleating agent, a weather-resistant agent and a lubricating agent in a high-speed mixer according to a certain mass ratio, putting the mixture into a double-screw extruder, and extruding and granulating the mixture for later use;
step 2, freezing and crushing the mixture obtained in the step 1 by nitrogen, grinding by a ball mill, and screening by an air flow classifier to obtain a small-particle-size polypropylene powder raw material;
step 3, 0.1 to 0.5 portion of nano Al is added by weight2O3Adding into absolute ethanol, adding 0.01-0.03 part of coupling agent KH550, and ultrasonically dispersing for 2-4h to obtain dispersion; adding the small-particle size polypropylene powder raw material obtained in the step 2 into the dispersion liquid, and quickly stirring to ensure that the nano Al is obtained2O3Coated on polypropyleneFiltering out the product on the surface of the olefin powder, drying and screening to obtain polypropylene powder;
and 4, adding the polypropylene powder obtained in the step 3, an antistatic agent and hydrophobic fumed silica into a double-motion mixer in parts by weight, and mixing to obtain the polypropylene powder material for selective laser sintering 3D printing.
In one embodiment, the preparation method of the polypropylene raw material in the step 1 comprises the following steps: mixing 100 parts of polypropylene, 2-4 parts of tetramethyl tetravinylcyclotetrasiloxane (D4vi), 0.5-1 part of initiator, 0.1-0.2 part of catalyst and 1-3 parts of grafting aid by weight parts, and performing reactive extrusion through a double-screw extruder to obtain polypropylene subjected to silane crosslinking condensation treatment, wherein the operating conditions of the double-screw extruder are as follows: the screw rotation speed is 80-120r/min, and the temperature of the heating area is 185-205 ℃.
In one embodiment, the polypropylene is a block copolymer polypropylene having an ethylene content of 8 to 10% and a melt index MFR (230 ℃, 2.16 kg) of 15 to 30.
In one embodiment, the initiator is benzoyl peroxide; the catalyst is an organic tin catalyst; the grafting assistant is divinylbenzene.
In one embodiment, the raw material particle size distribution of the small-particle size polypropylene powder is D10=30-50um, D50=80-100um, D90=130-150 um.
Advantageous effects
(1) In the invention, preferably, a polypropylene material modified by tetramethyltetravinylcyclotetrasiloxane (D4vi) is adopted, tetramethyltetravinylcyclotetrasiloxane (D4vi) is taken as a modifying material, mixed with a cross-linking agent, a catalyst and an initiator, and then synchronously reacted through a screw extrusion process, condensation reaction of tetramethyltetravinylcyclotetrasiloxane firstly occurs, and the material is cross-linked with polypropylene through unsaturated bonds under the action of the initiator to form a complex three-dimensional space network structure consisting of a ring structure formed by D4 and a cross-linking structure between PP-D4, so that the material can be effectively suitable for a 3D printing operation process, and the material obtained after printing has smaller brittleness and better toughness.
(2) The invention also comprises the maleic anhydride grafted POE which has better plasticity and processability and can effectively improve the toughness of the material after 3D printing. The modified polypropylene has reduced crystallization property and crystal form size, so that the warpage of the material in the sintering process can be improved, the toughness of the material is improved, the impact resistance is good, and a product with practical value can be prepared by selective laser sintering.
(3) According to the invention, polyquaternium and hydrophobic fumed silica are added, so that the flowability of the powder is improved, and the problems of fluffiness and poor flowability caused by static electricity generated in the process of mixing and conveying the powder to a printer are avoided.
(4) In the invention, firstly, mixing and extruding and mixing processing are carried out by using a screw extruder; then, the polypropylene material can be crushed into powder with smaller granularity after the cryogenic crushing treatment, and then the powder and the heat conducting particles Al are mixed in a liquid phase mode2O3The coating is carried out, and Al can be effectively improved by using the silane coupling agent2O3And fusing polypropylene material powder; the modified polypropylene powder is easier to form a heat conduction network in the sintering process, so that the polypropylene powder can efficiently absorb heat and melt, a good fusion effect is achieved, and meanwhile, the polypropylene powder can be rapidly cooled and molded, so that a sintered product has good physical and mechanical properties.
Detailed Description
Example 1
100 parts of polypropylene resin (with the vinyl content of 9.0 and the MFR 18), 10 parts of maleic anhydride grafted POE, 3 parts of N, N' -dicyclohexyl terephthalamide, 1.5 parts of antioxidant 1010, 1.5 parts of light stabilizer 770 and 3 parts of stearic acid are uniformly mixed in a high-speed mixer, and the mixture is put into a double-screw extruder to be extruded and granulated for later use.
And (3) freezing and crushing the obtained polypropylene particles by adopting liquid nitrogen, grinding the obtained polypropylene particles by using a ball mill, and screening the obtained polypropylene particles by using an air classifier to obtain a polypropylene powder raw material, wherein the particle size distribution of the polypropylene powder raw material is D10=43um, D50=92um and D90=147 um.
0.1 part of nano Al2O3Adding into anhydrous ethanol, adding 0.01 part of coupling agent KH550, ultrasonically dispersing for 2h to obtain dispersion, adding 100 parts of polypropylene powder obtained in the previous step into the dispersion, and rapidly stirring for 3h to obtain nano Al2O3Coating the surface of polypropylene powder, suction filtering, drying, and sieving to obtain nano Al2O3The coated polypropylene powder is ready for use.
And adding 100 parts of the powder obtained in the previous step, 0.1 part of antistatic agent polyquaternium and 0.2 part of hydrophobic fumed silica into a double-motion mixer, and mixing for 10min to obtain the polypropylene powder material for selective laser sintering 3D printing.
Example 2
100 parts of polypropylene resin (with the vinyl content of 9.0 and the MFR 18), 8 parts of maleic anhydride grafted POE, 5 parts of N, N' -dicyclohexyl terephthalamide, 2 parts of antioxidant 168, 2 parts of light stabilizer 770 and 5 parts of polyethylene wax are uniformly mixed in a high-speed mixer, and the mixture is put into a double-screw extruder to be extruded and granulated for later use.
And (3) freezing and crushing the obtained polypropylene particles by adopting liquid nitrogen, grinding the obtained polypropylene particles by using a ball mill, and screening the obtained polypropylene particles by using an air classifier to obtain a polypropylene powder raw material, wherein the particle size distribution of the polypropylene powder raw material is D10=38um, D50=86um and D90=133 um.
0.5 part of nano Al2O3Adding into absolute ethyl alcohol, adding 0.03 part of coupling agent KH550, performing ultrasonic dispersion for 4h to obtain dispersion, adding 100 parts of polypropylene powder obtained in the previous step into the dispersion, and rapidly stirring for 4h to obtain nano Al2O3Coating the surface of polypropylene powder, suction filtering, drying, and sieving to obtain nano Al2O3The coated polypropylene powder is ready for use.
And adding 100 parts of the powder obtained in the previous step, 0.2 part of antistatic agent polyquaternium and 0.4 part of hydrophobic fumed silica into a double-motion mixer, and mixing for 15min to obtain the polypropylene powder material for selective laser sintering 3D printing.
Example 3
100 parts of polypropylene resin (10.0 of vinyl content and MFR 30), 9 parts of maleic anhydride grafted POE, 3 parts of N, N' -dicyclohexyl terephthalamide, 2.5 parts of antioxidant 168, 2.5 parts of light stabilizer 328 and 4 parts of butyl stearate are uniformly mixed in a high-speed mixer, and the mixture is put into a double-screw extruder to be extruded and granulated for later use.
And (3) freezing and crushing the obtained polypropylene particles by adopting liquid nitrogen, grinding the obtained polypropylene particles by using a ball mill, and screening the obtained polypropylene particles by using an air classifier to obtain a polypropylene powder raw material, wherein the particle size distribution of the polypropylene powder raw material is D10=46um, D50=97um and D90=148 um.
0.3 part of nano Al2O3Adding into absolute ethyl alcohol, adding 0.02 part of coupling agent KH550, performing ultrasonic dispersion for 3h to obtain dispersion, adding 100 parts of polypropylene powder obtained in the previous step into the dispersion, and rapidly stirring for 4h to obtain nano Al2O3Coating the surface of polypropylene powder, suction filtering, drying, and sieving to obtain nano Al2O3The coated polypropylene powder is ready for use.
And adding 100 parts of the powder obtained in the previous step, 0.3 part of antistatic agent polyquaternium and 0.3 part of hydrophobic fumed silica into a double-motion mixer, and mixing for 15min to obtain the polypropylene powder material for selective laser sintering 3D printing.
Example 4
Compared to example 3, a silicone condensation crosslinked polypropylene was used.
Mixing 100 parts of polypropylene resin (with the vinyl content of 9.0 and the MFR 18), 2 parts of tetramethyl tetravinylcyclotetrasiloxane (D4vi), 0.5 part of benzoyl peroxide, 0.1 part of organic tin catalyst and 1 part of divinylbenzene, and then carrying out reactive extrusion by using a double-screw extruder, wherein the screw rotating speed is 80r/min, the heating area temperature is 195 ℃, and the polypropylene after silane crosslinking condensation treatment is obtained after extrusion operation; and uniformly mixing the obtained polypropylene subjected to silane crosslinking condensation treatment, 10 parts of maleic anhydride grafted POE, 3 parts of N, N' -dicyclohexyl terephthalamide, 1.5 parts of antioxidant 1010, 1.5 parts of light stabilizer 770 and 3 parts of stearic acid in a high-speed mixer, putting into a double-screw extruder, and extruding and granulating for later use.
And (3) freezing and crushing the obtained polypropylene particles by adopting liquid nitrogen, grinding the obtained polypropylene particles by using a ball mill, and screening the obtained polypropylene particles by using an air classifier to obtain a polypropylene powder raw material, wherein the particle size distribution of the polypropylene powder raw material is D10=43um, D50=92um and D90=147 um.
0.1 part of nano Al2O3Adding into anhydrous ethanol, adding 0.01 part of coupling agent KH550, ultrasonically dispersing for 2h to obtain dispersion, adding 100 parts of polypropylene powder obtained in the previous step into the dispersion, and rapidly stirring for 3h to obtain nano Al2O3Coating the surface of polypropylene powder, suction filtering, drying, and sieving to obtain nano Al2O3The coated polypropylene powder is ready for use.
And adding 100 parts of the powder obtained in the previous step, 0.1 part of antistatic agent polyquaternium and 0.2 part of hydrophobic fumed silica into a double-motion mixer, and mixing for 10min to obtain the polypropylene powder material for selective laser sintering 3D printing.
Example 5
Compared with example 2, the silicone condensation crosslinked polypropylene was used.
Mixing 100 parts of polypropylene resin (with the vinyl content of 9.0 and the MFR 18), 4 parts of tetramethyl tetravinylcyclotetrasiloxane (D4vi), 1 part of benzoyl peroxide, 0.2 part of organic tin catalyst and 3 parts of divinylbenzene, and then carrying out reactive extrusion by using a double-screw extruder, wherein the rotating speed of a screw in the extrusion process is 80-120r/min, the temperature of a heating area is 200 ℃, and the polypropylene after silane crosslinking condensation treatment is obtained after extrusion operation; and uniformly mixing the obtained polypropylene subjected to silane crosslinking condensation treatment, 8 parts of maleic anhydride grafted POE, 5 parts of N, N' -dicyclohexyl terephthalamide, 2 parts of antioxidant 168, 2 parts of light stabilizer 770 and 5 parts of polyethylene wax in a high-speed mixer, putting into a double-screw extruder, and extruding and granulating for later use.
And (3) freezing and crushing the obtained polypropylene particles by adopting liquid nitrogen, grinding the obtained polypropylene particles by using a ball mill, and screening the obtained polypropylene particles by using an air classifier to obtain a polypropylene powder raw material, wherein the particle size distribution of the polypropylene powder raw material is D10=38um, D50=86um and D90=133 um.
0.5 part of nano Al2O3Adding into absolute ethyl alcohol, adding 0.03 part of coupling agent KH550, performing ultrasonic dispersion for 4h to obtain dispersion, adding 100 parts of polypropylene powder obtained in the previous step into the dispersion, and rapidly stirring for 4h to obtain nano Al2O3Coating the surface of polypropylene powder, suction filtering, drying, and sieving to obtain nano Al2O3The coated polypropylene powder is ready for use.
And adding 100 parts of the powder obtained in the previous step, 0.2 part of antistatic agent polyquaternium and 0.4 part of hydrophobic fumed silica into a double-motion mixer, and mixing for 15min to obtain the polypropylene powder material for selective laser sintering 3D printing.
Example 6
Compared to example 3, a silicone condensation crosslinked polypropylene was used.
Mixing 100 parts of polypropylene resin (with the vinyl content of 10.0 and the MFR 30), 3 parts of tetramethyl tetravinylcyclotetrasiloxane (D4vi), 0.6 part of benzoyl peroxide, 0.15 part of organic tin catalyst and 2 parts of divinylbenzene, and then carrying out reactive extrusion by using a double-screw extruder, wherein the screw rotation speed is 110r/min and the heating area temperature is 195 ℃ in the extrusion process, and the polypropylene subjected to silane crosslinking condensation treatment is obtained after the extrusion operation; and uniformly mixing the obtained polypropylene subjected to silane crosslinking condensation treatment, 9 parts of maleic anhydride grafted POE, 3 parts of N, N' -dicyclohexyl terephthalamide, 2.5 parts of antioxidant 168, 2.5 parts of light stabilizer 328 and 4 parts of butyl stearate in a high-speed mixer, putting into a double-screw extruder, and extruding and granulating for later use.
And (3) freezing and crushing the obtained polypropylene particles by adopting liquid nitrogen, grinding the obtained polypropylene particles by using a ball mill, and screening the obtained polypropylene particles by using an air classifier to obtain a polypropylene powder raw material, wherein the particle size distribution of the polypropylene powder raw material is D10=46um, D50=97um and D90=148 um.
0.3 part of nano Al2O3Adding into absolute ethyl alcohol, adding 0.02 part of coupling agent KH550, performing ultrasonic dispersion for 3h to obtain dispersion, adding 100 parts of polypropylene powder obtained in the previous step into the dispersion, and rapidly stirring for 4h to obtain nano Al2O3Watch coated with polypropylene powderKneading, suction filtering, stoving and sieving to obtain nanometer Al powder2O3The coated polypropylene powder is ready for use.
And adding 100 parts of the powder obtained in the previous step, 0.3 part of antistatic agent polyquaternium and 0.3 part of hydrophobic fumed silica into a double-motion mixer, and mixing for 15min to obtain the polypropylene powder material for selective laser sintering 3D printing.
Comparative example 1
The preparation method is the same as that of example 1, except that no maleic anhydride grafted POE is added in the polypropylene modification process.
100 parts of polypropylene resin (with a vinyl content of 9.0 and MFR 18), 3 parts of N, N' -dicyclohexylterephthalamide, 1.5 parts of antioxidant 1010, 1.5 parts of light stabilizer 770 and 3 parts of stearic acid are uniformly mixed in a high-speed mixer, and the mixture is put into a double-screw extruder to be extruded and granulated for later use.
And (3) freezing and crushing the obtained polypropylene particles by adopting liquid nitrogen, grinding the obtained polypropylene particles by using a ball mill, and screening the obtained polypropylene particles by using an air classifier to obtain a polypropylene powder raw material, wherein the particle size distribution of the polypropylene powder raw material is D10=43um, D50=92um and D90=147 um.
0.1 part of nano Al2O3Adding into anhydrous ethanol, adding 0.01 part of coupling agent KH550, ultrasonically dispersing for 2h to obtain dispersion, adding 100 parts of polypropylene powder obtained in the previous step into the dispersion, and rapidly stirring for 3h to obtain nano Al2O3Coating the surface of polypropylene powder, suction filtering, drying, and sieving to obtain nano Al2O3The coated polypropylene powder is ready for use.
And adding 100 parts of the powder obtained in the previous step, 0.1 part of antistatic agent polyquaternium and 0.2 part of hydrophobic fumed silica into a double-motion mixer, and mixing for 10min to obtain the polypropylene powder material for selective laser sintering 3D printing.
Comparative example 2
The preparation method is the same as that of the example 1, except that the nucleating agent N, N' -dicyclohexyl terephthalamide is not added in the polypropylene modification process.
100 parts of polypropylene resin (with a vinyl content of 9.0 and MFR 18), 10 parts of maleic anhydride grafted POE, 1.5 parts of antioxidant 1010, 1.5 parts of light stabilizer 770 and 3 parts of stearic acid are uniformly mixed in a high-speed mixer, and the mixture is put into a double-screw extruder to be extruded and granulated for later use.
And (3) freezing and crushing the obtained polypropylene particles by adopting liquid nitrogen, grinding the obtained polypropylene particles by using a ball mill, and screening the obtained polypropylene particles by using an air classifier to obtain a polypropylene powder raw material, wherein the particle size distribution of the polypropylene powder raw material is D10=43um, D50=92um and D90=147 um.
0.1 part of nano Al2O3Adding into anhydrous ethanol, adding 0.01 part of coupling agent KH550, ultrasonically dispersing for 2h to obtain dispersion, adding 100 parts of polypropylene powder obtained in the previous step into the dispersion, and rapidly stirring for 3h to obtain nano Al2O3Coating the surface of polypropylene powder, suction filtering, drying, and sieving to obtain nano Al2O3The coated polypropylene powder is ready for use.
And adding 100 parts of the powder obtained in the previous step, 0.1 part of antistatic agent polyquaternium and 0.2 part of hydrophobic fumed silica into a double-motion mixer, and mixing for 10min to obtain the polypropylene powder material for selective laser sintering 3D printing.
Comparative example 3
The preparation method is the same as that of the example 1, except that nano Al is not carried out2O3Coating modified polypropylene powder.
100 parts of polypropylene resin (with the vinyl content of 9.0 and the MFR 18), 10 parts of maleic anhydride grafted POE, 3 parts of N, N' -dicyclohexyl terephthalamide, 1.5 parts of antioxidant 1010, 1.5 parts of light stabilizer 770 and 3 parts of stearic acid are uniformly mixed in a high-speed mixer, and the mixture is put into a double-screw extruder to be extruded and granulated for later use.
And (3) freezing and crushing the obtained polypropylene particles by adopting liquid nitrogen, grinding the obtained polypropylene particles by using a ball mill, and screening the obtained polypropylene particles by using an air classifier to obtain a polypropylene powder raw material, wherein the particle size distribution of the polypropylene powder raw material is D10=43um, D50=92um and D90=147 um.
And adding 100 parts of the powder obtained in the previous step, 0.1 part of antistatic agent polyquaternium and 0.2 part of hydrophobic fumed silica into a double-motion mixer, and mixing for 10min to obtain the polypropylene powder material for selective laser sintering 3D printing.
Comparative example 4
The preparation method is the same as that of example 1, except that no polyquaternium is added in the preparation of the polypropylene powder material.
100 parts of polypropylene resin (with the vinyl content of 9.0 and the MFR 18), 10 parts of maleic anhydride grafted POE, 3 parts of N, N' -dicyclohexyl terephthalamide, 1.5 parts of antioxidant 1010, 1.5 parts of light stabilizer 770 and 3 parts of stearic acid are uniformly mixed in a high-speed mixer, and the mixture is put into a double-screw extruder to be extruded and granulated for later use.
And (3) freezing and crushing the obtained polypropylene particles by adopting liquid nitrogen, grinding the obtained polypropylene particles by using a ball mill, and screening the obtained polypropylene particles by using an air classifier to obtain a polypropylene powder raw material, wherein the particle size distribution of the polypropylene powder raw material is D10=43um, D50=92um and D90=147 um.
0.1 part of nano Al2O3Adding into anhydrous ethanol, adding 0.01 part of coupling agent KH550, ultrasonically dispersing for 2h to obtain dispersion, adding 100 parts of polypropylene powder obtained in the previous step into the dispersion, and rapidly stirring for 3h to obtain nano Al2O3Coating the surface of polypropylene powder, suction filtering, drying, and sieving to obtain nano Al2O3The coated polypropylene powder is ready for use.
And adding 100 parts of the powder obtained in the previous step and 0.2 part of hydrophobic fumed silica into a double-motion mixer, and mixing for 10min to obtain the polypropylene powder material for selective laser sintering 3D printing.
Comparative example 5
The preparation method is the same as that of example 1, except that hydrophobic fumed silica is not added in the preparation of the polypropylene powder material.
100 parts of polypropylene resin (with the vinyl content of 9.0 and the MFR 18), 10 parts of maleic anhydride grafted POE, 3 parts of N, N' -dicyclohexyl terephthalamide, 1.5 parts of antioxidant 1010, 1.5 parts of light stabilizer 770 and 3 parts of stearic acid are uniformly mixed in a high-speed mixer, and the mixture is put into a double-screw extruder to be extruded and granulated for later use.
And (3) freezing and crushing the obtained polypropylene particles by adopting liquid nitrogen, grinding the obtained polypropylene particles by using a ball mill, and screening the obtained polypropylene particles by using an air classifier to obtain a polypropylene powder raw material, wherein the particle size distribution of the polypropylene powder raw material is D10=43um, D50=92um and D90=147 um.
0.1 part of nano Al2O3Adding into anhydrous ethanol, adding 0.01 part of coupling agent KH550, ultrasonically dispersing for 2h to obtain dispersion, adding 100 parts of polypropylene powder obtained in the previous step into the dispersion, and rapidly stirring for 3h to obtain nano Al2O3Coating the surface of polypropylene powder, suction filtering, drying, and sieving to obtain nano Al2O3The coated polypropylene powder is ready for use.
And adding 100 parts of the powder obtained in the previous step and 0.1 part of antistatic agent polyquaternium into a double-motion mixer, and mixing for 10min to obtain the polypropylene powder material for selective laser sintering 3D printing.
And carrying out selective laser sintering on the powder materials in the above embodiments and comparative examples, designing a model, setting printing parameters, carrying out laser sintering, cleaning powder, polishing and polarizing to obtain the piezoelectric polyurethane product. The powder bed temperature in the laser printing process is 120 ℃, and the laser energy is 0.10J/mm2。
The sintering process and the properties of the sintered article are shown in table 1.
TABLE 1 Properties of sintered articles of examples and comparative examples
As can be seen from the table above, the polypropylene material which can be applied to selective laser sintering 3D printing is successfully prepared by the method, and has good mechanical properties. Compared with the embodiment 4, the embodiment 1 can see that after the polypropylene material is modified by adopting tetramethyltetravinylcyclotetrasiloxane (D4vi), on one hand, the strength performance of the 3D printing material is improved after condensation reaction of siloxane, and simultaneously, due to the fact that D4vi can be crosslinked with polypropylene, after reaction extrusion, a complex three-dimensional space network structure is formed between PP-D4, and the elongation of the material is improved. As can be seen by comparing example 1 with comparative example 1, the method for printing in 3D is adopted in the patentThe material uses the maleic anhydride grafted POE, which has better plasticity and processability, can effectively improve the toughness of the 3D printed material, and obviously improves the elongation; as can be seen from the comparison between example 1 and comparative example 2, the nucleating agent can accelerate the crystallization speed, promote the molding and make the physical strength of the obtained material higher; as can be seen from the comparison between example 1 and comparative example 3, the polypropylene is micronized in the preparation process, and then the micronized polypropylene can be effectively mixed with Al2O3The polypropylene powder can efficiently absorb heat to melt, thereby achieving good fusion effect, and simultaneously can be rapidly cooled and molded, thereby enabling the sintered product to have good physical and mechanical properties. As can be seen from the comparison between the embodiment 1 and the comparative examples 4 and 5, the polyquaternium and the hydrophobic fumed silica improve the flowability of the powder, so that the problems of fluffy and poor flowability caused by static electricity in the printing process are avoided, and the physical properties of the material are improved.
Claims (10)
1. A polypropylene powder for selective laser sintering 3D printing is characterized by comprising the following components in parts by weight: 100 parts of polypropylene resin, 8-10 parts of maleic anhydride grafted POE, 3-5 parts of nucleating agent, 3-5 parts of weather-resistant agent, 3-5 parts of lubricant, 0.1-0.5 part of antistatic agent and 0.2-0.4 part of hydrophobic fumed silica.
2. The polypropylene powder for selective laser sintering 3D printing according to claim 1, wherein in one embodiment the polypropylene resin is cross-linked condensation treated with tetramethyltetravinylcyclotetrasiloxane (D4 vi).
3. The polypropylene powder for selective laser sintering 3D printing according to claim 1, wherein in one embodiment the polypropylene powder is further loaded with thermally conductive particles;
in one embodiment, the thermally conductive particles are Al2O3。
4. The polypropylene powder for selective laser sintering 3D printing according to claim 1, wherein in one embodiment the nucleating agent is one of N, N' -dicyclohexylterephthalamide, calcium suberate, calcium pimelate;
in one embodiment, the weathering agent is an antioxidant and light stabilizer 1: 1, a compounding system;
in one embodiment, the antioxidant is antioxidant 1010, antioxidant 168;
in one embodiment, the light stabilizers are light stabilizer 770, light stabilizer 328;
in one embodiment, the lubricant is one or a mixture of two of stearic acid, butyl stearate, PE wax and silicone powder;
in one embodiment, the antistatic agent is a polyquaternium.
5. The method of preparing polypropylene powder for selective laser sintering 3D printing according to claim 1, comprising the steps of:
step 1, uniformly mixing polypropylene resin, maleic anhydride grafted POE, a nucleating agent, a weather-resistant agent and a lubricating agent in a high-speed mixer according to a certain mass ratio, putting the mixture into a double-screw extruder, and extruding and granulating the mixture for later use;
step 2, freezing and crushing the mixture obtained in the step 1 by nitrogen, grinding by a ball mill, and screening by an air flow classifier to obtain a small-particle-size polypropylene powder raw material;
step 3, 0.1 to 0.5 portion of nano Al is added by weight2O3Adding into absolute ethanol, adding 0.01-0.03 part of coupling agent KH550, and ultrasonically dispersing for 2-4h to obtain dispersion; adding the small-particle size polypropylene powder raw material obtained in the step 2 into the dispersion liquid, and quickly stirring to ensure that the nano Al is obtained2O3Coating the surface of polypropylene powder, filtering, drying and screening the product to obtain polypropylene powder;
and 4, adding the polypropylene powder obtained in the step 3, an antistatic agent and hydrophobic fumed silica into a double-motion mixer in parts by weight, and mixing to obtain the polypropylene powder material for selective laser sintering 3D printing.
6. The method of preparing polypropylene powder for selective laser sintering 3D printing according to claim 5, wherein in one embodiment, the method of preparing polypropylene raw material in step 1 comprises the steps of: according to the weight portion, 100 portions of polypropylene, 2 to 4 portions of tetramethyl tetravinylcyclotetrasiloxane (D4vi), 0.5 to 1 portion of initiator, 0.1 to 0.2 portion of catalyst and 1 to 3 portions of grafting auxiliary agent are mixed and extruded by a double screw extruder to obtain the polypropylene after silane crosslinking condensation treatment.
7. The method of claim 5, wherein in one embodiment the polypropylene is a block copolymer polypropylene, having an ethylene content of 8-10%, a melt index MFR (230 ℃, 2.16 kg) of 15-30;
in one embodiment, the initiator is benzoyl peroxide; the catalyst is an organic tin catalyst; the grafting assistant is divinylbenzene.
8. The method for preparing polypropylene powder for selective laser sintering 3D printing according to claim 5, wherein in one embodiment, the operating conditions of the twin screw extruder are: the screw rotation speed is 80-120r/min, and the temperature of the heating area is 185-205 ℃.
9. The method of claim 5, wherein the raw material of the small-particle size polypropylene powder has a particle size distribution of D10=30-50um, D50=80-100um, D90=130-150 um.
10. Use of the polypropylene powder according to claim 1 for 3D printing.
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