CN104592626A - Spraying-free polypropylene composite material applicable for 3D print and preparation method thereof - Google Patents
Spraying-free polypropylene composite material applicable for 3D print and preparation method thereof Download PDFInfo
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- CN104592626A CN104592626A CN201410828785.1A CN201410828785A CN104592626A CN 104592626 A CN104592626 A CN 104592626A CN 201410828785 A CN201410828785 A CN 201410828785A CN 104592626 A CN104592626 A CN 104592626A
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- composite material
- spray
- polypropylene composite
- printing according
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 52
- -1 polypropylene Polymers 0.000 title claims abstract description 52
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000002667 nucleating agent Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000011256 inorganic filler Substances 0.000 claims abstract description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 4
- 239000003381 stabilizer Substances 0.000 claims abstract description 4
- 238000010146 3D printing Methods 0.000 claims description 27
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 239000003963 antioxidant agent Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000007580 dry-mixing Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 239000012745 toughening agent Substances 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000005368 silicate glass Substances 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 11
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 238000010008 shearing Methods 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000001746 injection moulding Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 11
- LNKJESSHRFPVPE-UHFFFAOYSA-N 5-(diethylamino)pentyl 3,4,5-trimethoxybenzoate;hydrochloride Chemical compound Cl.CCN(CC)CCCCCOC(=O)C1=CC(OC)=C(OC)C(OC)=C1 LNKJESSHRFPVPE-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 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 compound 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 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 241000282376 Panthera tigris Species 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical group C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- VKJLYEDTHCTCOH-UHFFFAOYSA-N 3-(3-octadecoxy-3-oxopropyl)sulfanylpropanoic acid Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(O)=O VKJLYEDTHCTCOH-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
- B29C48/92—Measuring, controlling or regulating
-
- 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
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
-
- 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
-
- 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
- B29C2948/92704—Temperature
-
- 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
- C08L2205/24—Crystallisation aids
- C08L2205/242—Beta spherulite nucleating agents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a spraying-free polypropylene composite material applicable for 3D print and a preparation method thereof. The composite material is prepared from the following raw materials in percentage by weight: 60-94% of polypropylene, 5-20% of toughing agent, 0-20% of inorganic filler, 0.1-0.5% of nucleating agent, 0.2-2% of metal powder, 0.2-2% of pearl powder, 0.2-2% of stabilizer, and 0-5% of other additive. The composite material and the preparation method thereof have the following advantages: 1, the spraying-free polypropylene composite material applicable for 3D print with low shrinkage, none warping, attractive gloss, excellent rigidity and toughness, very high metal texture and pearl effect is prepared, and the composite material is important for the development of 3D print materials; 2, the shearing and dispersion of inorganic filler, nucleating agent, toughing agent, metal powder and pearl powder are improved furthest, and the performance of the composite material is improved further.
Description
Technical Field
The invention relates to a polypropylene composite material, in particular to a spraying-free polypropylene composite material for 3D printing and a preparation method of the composite material, and belongs to the field of polymer modification and processing.
Background
The rapid prototyping technology is also called 3D printing technology, is born in the late 80 s of the 20 th century, and is a high-tech manufacturing technology based on a material accumulation method. An important branch of 3D printing is personal printing that has emerged since around 2008. Most personal 3D printers use FDM (Fused Deposition Modeling) to perform printing. The basic principle of the technology is that thermoplastic polymer filaments (the matching diameter of the current mainstream printer is 1.75mm and 3mm) are conveyed to a high-temperature hot end by a gear to melt the polymer and continuously extrude the molten polymer, and a three-dimensional object is constructed in a layer-by-layer stacking mode under accurate positioning.
Polypropylene has good processability and physical and chemical properties, extremely low density, and relatively low cost, and is widely used and currently the most rapidly growing general purpose thermoplastic. However, most of polypropylene has poor toughness, large shrinkage rate and low crystallization speed, and the product is easy to shrink to generate deformation and warpage, is slightly brittle and the like when 3D printing is adopted.
In order to meet the increasingly improved aesthetic requirements, many polypropylene materials need to be sprayed to achieve the effects of high gloss, metal texture and the like. However, polypropylene itself is difficult to spray and has complex process due to poor polarity and small surface tension.
Thus, the Chinese patent application CN201210036011.6 discloses a spray-free polypropylene composition with paint gloss and metal texture and a preparation method thereof, and the patent uses flake aluminum powder and color brightening agent in a matching way, so that the material has good paint gloss and metal texture, and the appearance is similar to the paint spraying effect.
The Chinese invention patent CN201210509606.9 discloses a spray-free polypropylene material with high gloss and metallic or pearlescent glitter effect, which uses random copolymerization propylene and effect pigment to make PP of the invention obtain good gloss and pearlescent glitter without spray-direct injection molding, and metallic spray-painting effect.
The Chinese invention patent CN201310535116.0 discloses a spray-free modified polypropylene material with paint bright silver metal texture, which uses spherical aluminum powder to solve the problem that flaky aluminum powder modified materials are easy to generate tiger skin lines.
The Chinese invention patent CN201310670823.0 discloses a spraying-free scratch-resistant polypropylene material for automotive upholsteries and a preparation method thereof, and the problems of flow marks, welding lines and the like of the material are improved through a compatilizer and silver element type flaky aluminum powder.
Due to the particularity of the processing mode of the 3D printing, the problems of weld lines, flow marks, tiger skin stripes and the like cannot be caused, but higher requirements on toughness, shrinkage rate, crystallization speed and the like are met. The polypropylene composite material which has low density, high gloss, metal texture, low shrinkage and good toughness and can be used for 3D printing is provided, and the polypropylene composite material has important significance for promoting the development of 3D printing materials.
Disclosure of Invention
The invention aims to develop a modified polypropylene composite material with metal texture, high toughness and low shrinkage so as to overcome the limitation of a 3D printing material.
Another object of the present invention is to provide a method for preparing such a polypropylene composite.
The purpose of the invention can be realized by the following technical scheme:
a spraying-free polypropylene composite material for 3D printing comprises the following raw materials in percentage by weight:
further, the spraying-free polypropylene composite material for 3D printing comprises the following raw materials in percentage by weight:
wherein,
the polypropylene is homopolymerized propylene or random copolymerization propylene with the melt flow rate (230 ℃ C. multiplied by 2.16kg) of 0.5-60g/10min, wherein the comonomer of the random copolymerization propylene is ethylene, and the content of the comonomer is in the range of 1-7%. Random copolymerized propylene having a melt flow rate (230 ℃ C. times.2.16 kg) of 3 to 40g/10min is preferred.
The toughening agent is any suitable ethylene-octene copolymer (POE), and the melt flow rate (190 ℃ multiplied by 2.16kg) is 0.5-50g/10 min.
The inorganic filler is one or more of ultra-pure superfine talcum powder, barium sulfate and the like, and the average grain diameter of the inorganic filler is 1-20 mu m; barium sulfate having an average particle diameter of 1 to 10 μm is preferable.
The nucleating agent is any suitable beta nucleating agent, including but not limited to Guangdong waring rare earth nucleating agent, TMB-5 of Shanxi chemical research institute, and the like.
The metal powder is one or more of gold powder, aluminum powder, silver powder and copper powder, and is preferably flaky aluminum powder with the average particle size of 5-20 mu m.
The pearl powder is one or a mixture of titanium dioxide coated mica and titanium dioxide coated silicate glass sheets. The average particle diameter is preferably 10 to 50 μm.
The stabilizer comprises a primary antioxidant and a secondary antioxidant, wherein the primary antioxidant is one or a combination of more of hindered phenol antioxidants and thioester antioxidants, including but not limited to a composition of one or more of 3114 (with the chemical name of 1,3, 5-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6[1H,3H,5H ] trione), 1010 (with the chemical name of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester), DSTP (with the chemical name of thiodipropionate stearyl ester); the auxiliary antioxidant is one or a combination of phosphite and ester antioxidants, and includes but is not limited to one or a combination of 618 (chemical name is dioctadecyl pentaerythritol diphosphite) and 168 (chemical name is tris (2, 4-di-tert-butyl) phosphite).
Other additives may also be included, including combinations of one or more of colorants, processing aids, lubricants, as deemed desirable by those skilled in the art.
The preparation method of the spraying-free polypropylene composite material for 3D printing comprises the following steps:
1) weighing the raw materials according to the weight ratio;
2) putting the step 1) into a high-speed mixer for dry mixing for 3-15 minutes, adding the mixed raw materials into a double-screw extruder, and cooling and granulating after melt extrusion;
wherein the temperature in the screw cylinder is as follows: the first zone is 180-.
The invention has the advantages that:
1. POE is used as a toughening agent for processing polypropylene, so that the toughness of the material can be efficiently improved, and the shrinkage rate of the material can be reduced; the beta nucleating agent is used for accelerating the crystallization speed, improving the forming speed, refining the spherulite size and simultaneously reducing the crystal area density (the common PP crystals mainly form alpha crystals with the density of 0.936 g/cm)3The beta nucleating agent promotes the conversion of alpha crystals into beta crystals with the density of 0.922g/cm3) The shrinkage rate is reduced; the high-number barium sulfate and the like are adopted, so that the shrinkage rate is reduced, high glossiness is kept, and the surface hardness can be improved; due to the advantages of the processing mode, the problems of flow marks and tiger stripes do not need to be considered, and compared with other effect pigments, the high-efficiency aluminum flake powder and the high-efficiency pearl flake powder are used, and only lower addition amount is needed to achieve the same effect. Has good comprehensive performance.
2. The feeding mode from the main feeding port is adopted, so that the shearing is enhanced, the dispersing effect of the toughening agent, the barium sulfate, the metal powder, the pearl powder and the like is improved, and the performance of the composite material is further improved.
Detailed Description
The present invention will be described in further detail with reference to examples. The scope of the invention is set forth in the claims and is not limited by these examples.
In the composite formulations of the examples and comparative examples, the polypropylene used was a random copolymer propylene having a melt flow rate (230 ℃ C. times.2.16 kg) of 3 to 40g/10min and an ethylene content of 1 to 7%.
The toughening agent is ethylene-octene copolymer (POE) or Dow POE 8150.
The inorganic filler is barium sulfate with spherical structure with average particle diameter of 1-10 μm.
The nucleating agent is a beta nucleating agent which is TMB-5 of Shanxi chemical research institute.
The metal powder used was an aluminum flake having an average particle diameter of 10 μm.
The pearl powder is a sheet-shaped titanium dioxide coated silicate glass sheet with the average grain diameter of 40 mu m.
The stabilizers used were Negonox DSTP (chemical name stearyl thiodipropionate) from ICE, British, Irganox 1010 (chemical name pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]) from Ciba, and Igrafos168 (chemical name tris (2, 4-di-tert-butylphenyl) phosphite) from Ciba.
Other additives used are combinations of one or more of colorants, processing aids, lubricants as deemed desirable by one skilled in the art.
Example 1
Weighing 88.1 percent of polypropylene, 10 percent of POE 8150, 0.2 percent of TMB-5, 0.2 percent of aluminum powder, 1 percent of pearl powder, 0.1 percent of Irganox 1010, 0.1 percent of Igrafos168 and 0.3 percent of Negonox DSTP according to the weight percentage, dry-mixing for 5 minutes in a high-speed mixer, adding into a double-screw extruder, melting, extruding and granulating, wherein the temperature in a screw cylinder is as follows: the first zone is 180 ℃, the second zone is 205 ℃, the third zone is 220 ℃, the fourth zone is 210 ℃, the head is 210 ℃, and the rotating speed of the double-screw extruder is 500 r/min. Drying the particles, and performing injection molding on an injection molding machine to prepare a sample.
Example 2
Weighing 66.3% of polypropylene, 10% of POE 8150, 20% of barium sulfate, 0.2% of TMB-5, 2% of aluminum powder, 1% of pearl powder, 0.1% of Irganox 1010, 0.1% of Igrafos168 and 0.3% of Negonox DSTP according to the weight percentage, dry-mixing for 5 minutes in a high-speed mixer, adding into a double-screw extruder, melting, extruding and granulating, wherein the temperature in a screw cylinder is as follows: the first zone is 180 ℃, the second zone is 205 ℃, the third zone is 220 ℃, the fourth zone is 210 ℃, the head is 210 ℃, and the rotating speed of the double-screw extruder is 500 r/min. Drying the particles, and performing injection molding on an injection molding machine to prepare a sample.
Example 3
Weighing 77.3% of polypropylene, 10% of POE 8150, 10% of barium sulfate, 0.2% of TMB-5, 1% of aluminum powder, 1% of pearl powder, 0.1% of Irganox 1010, 0.1% of Igrafos168 and 0.3% of Negonox DSTP according to the weight percentage, dry-mixing for 5 minutes in a high-speed mixer, adding into a double-screw extruder, and carrying out melt extrusion granulation, wherein the temperature in a screw cylinder is as follows: the first zone is 180 ℃, the second zone is 205 ℃, the third zone is 220 ℃, the fourth zone is 210 ℃, the head is 210 ℃, and the rotating speed of the double-screw extruder is 500 r/min. Drying the particles, and performing injection molding on an injection molding machine to prepare a sample.
Example 4
Weighing 83.1 percent of polypropylene, 5 percent of POE 8150, 10 percent of barium sulfate, 0.2 percent of TMB-5, 1 percent of aluminum powder, 0.2 percent of pearl powder, 0.1 percent of Irganox 1010, 0.1 percent of Igrafos168 and 0.3 percent of Negonox DSTP according to the weight percentage, dry-mixing for 5 minutes in a high-speed mixer, adding into a double-screw extruder for melt extrusion granulation, wherein the temperature in a screw cylinder is as follows: the first zone is 180 ℃, the second zone is 205 ℃, the third zone is 220 ℃, the fourth zone is 210 ℃, the head is 210 ℃, and the rotating speed of the double-screw extruder is 500 r/min. Drying the particles, and performing injection molding on an injection molding machine to prepare a sample.
Example 5
Weighing 66.3% of polypropylene, 20% of POE 8150, 10% of barium sulfate, 0.2% of TMB-5, 1% of aluminum powder, 2% of pearl powder, 0.1% of Irganox 1010, 0.1% of Igrafos168 and 0.3% of Negonox DSTP according to the weight percentage, dry-mixing for 5 minutes in a high-speed mixer, adding into a double-screw extruder, melting, extruding and granulating, wherein the temperature in a screw cylinder is as follows: the first zone is 180 ℃, the second zone is 205 ℃, the third zone is 220 ℃, the fourth zone is 210 ℃, the head is 210 ℃, and the rotating speed of the double-screw extruder is 500 r/min. Drying the particles, and performing injection molding on an injection molding machine to prepare a sample.
Comparative example 1
Weighing 78.3% of polypropylene, 10% of POE 8150, 10% of barium sulfate, 0.2% of TMB-5, 1% of aluminum powder, 0.1% of Irganox 1010, 0.1% of Igrafos168 and 0.3% of Negonox DSTP according to weight percentage, dry-mixing for 5 minutes in a high-speed mixer, adding into a double-screw extruder, and carrying out melt extrusion granulation, wherein the temperature in a screw cylinder is as follows: the first zone is 180 ℃, the second zone is 205 ℃, the third zone is 220 ℃, the fourth zone is 210 ℃, the head is 210 ℃, and the rotating speed of the double-screw extruder is 500 r/min. Drying the particles, and performing injection molding on an injection molding machine to prepare a sample.
Comparative example 2
Weighing 98.5 percent of polypropylene, 1 percent of pearl powder, 0.1 percent of Irganox 1010, 0.1 percent of Igrafos168 and 0.3 percent of Negonox DSTP according to weight percentage, dry mixing for 5 minutes in a high-speed mixer, adding into a double-screw extruder, melting, extruding and granulating, wherein the temperature in a screw cylinder is as follows: the first zone is 180 ℃, the second zone is 205 ℃, the third zone is 220 ℃, the fourth zone is 210 ℃, the head is 210 ℃, and the rotating speed of the double-screw extruder is 500 r/min. Drying the particles, and performing injection molding on an injection molding machine to prepare a sample.
Performance evaluation method:
the density of the sample is measured according to ISO1183A in g/cm3(ii) a The flexural Property test was carried out according to ISO178 StandardThe sample size is 80 multiplied by 10 multiplied by 4mm, the span is 64mm, the bending speed is 2mm/min, and the unit MPa; the impact performance of the simply supported beam is tested according to ISO179 standard, the size of a sample is 80 multiplied by 10 multiplied by 4mm, the depth of a gap is 2mm, and the unit Kj/m2(ii) a The material shrinkage is measured in accordance with ISO2577 in%.
The formulations and performance test results for the examples and comparative examples are shown in the following tables:
TABLE 1 Material formulations (wt.%) for examples 1-5 and comparative examples 1-2
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| PP | 88.1 | 66.3 | 77.3 | 83.1 | 66.3 | 78.3 | 98.5 |
| POE | 10 | 10 | 10 | 5 | 20 | 10 | 0 |
| Barium sulfate | 0 | 20 | 10 | 10 | 10 | 10 | 0 |
| TMB-5 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0 |
| Aluminum powder | 0.2 | 2 | 1 | 1 | 1 | 1 | 0 |
| Pearl powder | 1 | 1 | 1 | 0.2 | 2 | 0 | 1 |
| 1010 | 0.1 | 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 | 0.1 |
| DSTP | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
TABLE 2 results of Performance test of examples 1-5 and comparative examples 1-2
As can be seen from the comparison of comparative examples 1-2 and examples 1-5, the pearl powder provides pearl effect, while the aluminum flake powder gives the material a strong metallic texture. Meanwhile, the selected formula system has higher gloss which is close to the gloss of typical ABS. Wherein, the embodiment 3 has excellent mechanical property, and the metallic texture and the pearlescent effect are very obvious. Each embodiment is extruded into a 3mm line and used for FDM printing, and products which are not warped, good in precision and luster, and excellent in metal texture and pearly effect can be printed without using a hot bed.
Claims (15)
1. The utility model provides a exempt from to spray polypropylene composite that can be used to 3D printing which characterized in that: the composite material consists of the following raw materials in percentage by weight:
2. the spray-free polypropylene composite material useful for 3D printing according to claim 1, wherein: the composite material consists of the following raw materials in percentage by weight:
3. the spray-free polypropylene composite material usable for 3D printing according to claim 1 or 2, wherein: the polypropylene has a melt flow rate of 0.5-60g/10min, and the comonomer of the random copolymerized propylene is ethylene, and the content of the comonomer is 1-7%.
4. The spray-free polypropylene composite material usable for 3D printing according to claim 3, wherein: the polypropylene has the melt flow rate of 3-40g/10min under the test conditions of 230 ℃ and 2.16 kg.
5. The spray-free polypropylene composite material usable for 3D printing according to claim 1 or 2, wherein: the toughening agent is ethylene-octene copolymer (POE), and the melt flow rate is 0.5-50g/10min under the test condition of 190 ℃ and 2.16 kg.
6. The spray-free polypropylene composite material usable for 3D printing according to claim 1 or 2, wherein: the inorganic filler is one or the combination of more than two of talcum powder and barium sulfate, and the average grain diameter of the inorganic filler is 1-20 mu m.
7. The spray-free polypropylene composite material usable for 3D printing according to claim 1 or 2, wherein: the nucleating agent is a beta nucleating agent.
8. The spray-free polypropylene composite material usable for 3D printing according to claim 1 or 2, wherein: the metal powder is one or more of copper powder, gold powder, silver powder and aluminum powder.
9. The spray-free polypropylene composite material useful for 3D printing according to claim 8, wherein: the metal powder is flaky aluminum powder with the average particle size of 5-20 mu m.
10. The spray-free polypropylene composite material usable for 3D printing according to claim 1 or 2, wherein: the pearl powder is one or a mixture of titanium dioxide coated mica powder and titanium dioxide coated silicate glass.
11. The spray-free polypropylene composite material useful for 3D printing according to claim 10, wherein: the pearl powder is flaky, and the average grain diameter is 10-50 mu m.
12. The spray-free polypropylene composite material usable for 3D printing according to claim 1 or 2, wherein: the stabilizer comprises a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is one or a mixture of hindered phenol and thioester antioxidants; the auxiliary antioxidant is one or more of phosphite and ester antioxidant.
13. The spray-free polypropylene composite material useful for 3D printing according to claim 12, wherein: the main antioxidant is one or the combination of more than two of 3114, 1010 and DSTP; the auxiliary antioxidant is one or two of 618 and 168.
14. The spray-free polypropylene composite material usable for 3D printing according to claim 1 or 2, wherein: other additives are also included, including combinations of one or more of colorants, processing aids, and lubricants as deemed desirable by those skilled in the art.
15. A method of preparing the spray-free polypropylene composite useful for 3D printing according to claim 1 or 2, comprising the steps of:
1) weighing the raw materials according to the weight ratio;
2) putting the raw materials obtained in the step 1) into a high-speed mixer for dry mixing for 3-15 minutes, adding the mixed raw materials into a double-screw extruder, and cooling and granulating after melt extrusion;
wherein the temperature in the screw cylinder is as follows: the first zone is 180-.
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