CN116285113A - 3D printing polypropylene material with high interlayer bonding interface and preparation method thereof - Google Patents
3D printing polypropylene material with high interlayer bonding interface and preparation method thereof Download PDFInfo
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- CN116285113A CN116285113A CN202310411463.6A CN202310411463A CN116285113A CN 116285113 A CN116285113 A CN 116285113A CN 202310411463 A CN202310411463 A CN 202310411463A CN 116285113 A CN116285113 A CN 116285113A
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- inorganic filler
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- polypropylene
- silane
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- -1 polypropylene Polymers 0.000 title claims abstract description 94
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 88
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 87
- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000010146 3D printing Methods 0.000 title claims abstract description 39
- 239000011229 interlayer Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 44
- 239000011256 inorganic filler Substances 0.000 claims description 33
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 33
- 239000002131 composite material Substances 0.000 claims description 26
- 239000003963 antioxidant agent Substances 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000008187 granular material Substances 0.000 claims description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims description 18
- 230000003078 antioxidant effect Effects 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 229910000077 silane Inorganic materials 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- 229920006243 acrylic copolymer Polymers 0.000 claims description 6
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 6
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 7
- 239000010410 layer Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229920005660 Nucrel® 2940 Polymers 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 2
- BESKSSIEODQWBP-UHFFFAOYSA-N 3-tris(trimethylsilyloxy)silylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C BESKSSIEODQWBP-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229920001410 Microfiber Polymers 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a 3D printing polypropylene material with a high interlayer bonding interface and a preparation method thereof, belonging to the technical field of preparation of 3D printing materials. The 3D printing polypropylene material has the advantages of high interlayer bonding interface strength, good toughness and the like, and is suitable for solving the technical problem of poor mechanical anisotropy and toughness of the traditional 3D printing polypropylene product.
Description
Technical Field
The invention belongs to the technical field of preparation of 3D printing, and relates to a 3D printing polypropylene material with a high interlayer bonding interface and a preparation method thereof.
Background
The fused deposition modeling (FDM technology) is formed by overlapping polymer melt filaments layer by layer, so that the limitation of the traditional processing modeling on the shape and structural design can be broken through, the microstructure of the thermoplastic polymer can be regulated and controlled, and a promising method is provided for near net shaping, flexible design and rapid verification of light high-strength parts in the fields of automobiles, medical treatment and the like. Polypropylene is an important general plastic, and can form self-reinforced structures such as microfibers, serial crystals, orientations and the like under the combined action of an FDM shearing field and a temperature field, so that high-toughness complex parts are rapidly manufactured, and the polypropylene is one of important materials for promoting the application of the FDM technology in different fields. However, the high cooling rates and complex temperature variations inherent in FDM processes often promote the formation of unpredictable crystalline structures and inadequate molecular chain topology entanglement of the polypropylene at the interlaminar interface, leading to weak and brittle interlaminar interfaces and significant mechanical property anisotropy, affecting its assembly accuracy and load carrying capacity.
At present, various techniques have been proposed mainly in terms of both process and material to enhance the interfacial properties between layers of polypropylene FDM molded parts. In terms of process, optimizing printing parameters, in-situ laser preheating, post-treatment and the like can improve interlayer interface strength and toughness by enhancing molecular chain movement capability and prolonging healing time. In terms of materials, a printing material is modified by a chemical and physical method (the invention patent CN 115785571A utilizes the strong cohesive strength and adhesive force of ester groups to improve the bonding strength between thin layers by adding low-melting-point polyester polyol into polypropylene resin, and the invention patent CN 111073160A adds an acrylic adhesive into polypropylene to improve the interlayer bonding strength by means of the strong polar groups of phenolic hydroxyl groups in the dopamine graft copolymer). But the interlayer bonding strength (9.37 MPa) and toughness of the modified material are far lower than the bulk strength of the polypropylene material.
Therefore, new modification methods, such as construction of a chemical bonding network structure at an interlayer interface to enhance interlayer interface performance of a 3D printed article, are required to be studied.
Disclosure of Invention
Accordingly, one of the objectives of the present invention is to provide a 3D printed polypropylene material with a high interlayer bonding interface; the second purpose of the invention is to provide a preparation method of the 3D printing polypropylene material with a high interlayer bonding interface.
In order to achieve the above purpose, the present invention provides the following technical solutions:
1. the 3D printing polypropylene material comprises, by weight, 70-90 parts of polypropylene, 10-20 parts of acrylic acid copolymer, 1-10 parts of modified inorganic filler and 0.1-1 part of antioxidant;
the modified inorganic filler is an inorganic filler with any one or more of thiol groups, epoxy groups, amino groups and hydroxyl groups on the surface, wherein the inorganic filler is any one or two of silicon dioxide or montmorillonite;
the antioxidant is any one or more of hindered phenol antioxidants, phosphorous acid antioxidants and alkyl ester antioxidants.
Preferably, the acid content of the acrylic copolymer is 4-10%, and the melt index measured under the test condition of 190 ℃/2.16Kg is 2-15 g/10min.
Further preferably, the melt index of the acrylic copolymer is 5 to 10g/10min when tested under the test condition of 190 ℃/2.16 Kg.
Further preferably, the acrylic acid copolymer is any one or more of ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene/ethyl acrylate copolymer or ethylene vinyl acetate copolymer.
Preferably, the modified inorganic filler is prepared according to the following method:
A. adding an inorganic filler into a solvent, and performing ultrasonic treatment to obtain an inorganic filler suspension, wherein the solvent is any one or more of toluene, dimethylbenzene, ethanol and water;
B. dropwise adding a silane organic compound into an inorganic filler suspension under the protection of nitrogen, and stirring at 100-120 ℃ for reacting for 2-24 hours, wherein the silane organic compound is any one or more of aminosilane, methacryloxy silane, epoxy silane, mercapto silane or long-chain silane, and the number of carbon atoms on a main chain in the long-chain silane is not less than 10;
C. after the reaction is finished, the residual silane organic compound is removed by ethanol cleaning, and the modified inorganic filler is obtained by vacuum drying for 2 to 24 hours at the temperature of between 25 and 120 ℃.
Further preferably, the mass ratio of the silane coupling agent to the inorganic filler is 1-3:1.
Preferably, the modified inorganic filler has an average particle diameter of 50 to 300nm.
Preferably, the antioxidant is a mixture of hindered phenol antioxidant 1010 and phosphite antioxidant 168 according to a mass ratio of 1:1.
2. The preparation method of the 3D printing polypropylene material comprises the following steps:
(1) According to the weight portions, mixing polypropylene, acrylic acid copolymer, modified inorganic filler and antioxidant, stirring uniformly, putting into a double screw, extruding after melting and mixing uniformly, granulating and drying to obtain polypropylene composite granules;
(2) And (3) putting the polypropylene composite granules into a single screw extruder, melting, extruding into a water bath at 25-50 ℃, and extruding filaments to obtain the 3D printing polypropylene material with the high interlayer bonding interface.
The invention has the beneficial effects that: the invention discloses a 3D printing polypropylene material with a high interlayer bonding interface, which comprises, by weight, 70-90 parts of polypropylene, 10-20 parts of an acrylic copolymer, 1-10 parts of a modified inorganic filler and 0.1-1 part of an antioxidant. The 3D printing polypropylene material has the advantages of high interlayer bonding interface strength, good toughness and the like, and is suitable for solving the technical problems of low interlayer bonding interface strength and poor toughness of the traditional 3D printing polypropylene.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objects and other advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the specification.
Drawings
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in the following preferred detail with reference to the accompanying drawings, in which:
FIG. 1 is a diagram showing the mechanism of chemical bond formation at the interlayer interface of the 3D printed polypropylene material with high interlayer bonding interface prepared in example 2;
fig. 2 is a 3D printed article obtained by 3D printing of the polypropylene material prepared in example 2 with high interlayer bonding interface.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention. It should be noted that the illustrations provided in the following embodiments merely illustrate the basic idea of the present invention by way of illustration, and the following embodiments and features in the embodiments may be combined with each other without conflict.
Example 1
The 3D printing polypropylene composite material with the high interlayer bonding interface is prepared according to the following method:
(1) Preparing modified inorganic filler: A. will be
Adding the synthesized silicon dioxide with the average sphere diameter of 300nm into toluene, and carrying out ultrasonic treatment to obtain a silicon dioxide suspension; B. under the protection of nitrogen, an epoxy silane coupling agent KH-560 (wherein the mass ratio of the epoxy silane coupling agent KH-560 to the silicon dioxide is 2:1) is dropwise added into the silicon dioxide suspension, and the mixture is stirred and reacted for 24 hours at 110 ℃; C. after the reaction, residual KH-560 was removed by washing with ethanol and dried under vacuum at 25℃for 12 hours to give silica having epoxy groups with an average particle size in the range of 50 to 300nm.
(2) Mixing 80 parts of polypropylene (1100N, ningpo), 10 parts of ethylene-methacrylic acid copolymer (EMAA, duPont Nucrel 2940), 10 parts of silicon dioxide with epoxy groups and 0.5 part of antioxidant (a mixture formed by phenol-blocking antioxidant 1010 and phosphite antioxidant 168 according to the mass ratio of 1:1), uniformly stirring, putting into a double screw, melting, uniformly mixing, extruding, granulating and drying to obtain polypropylene composite granules;
(3) The polypropylene composite granules are put into a single screw extruder, melted and extruded into a water bath at 40 ℃, and the 3D printing polypropylene material with the diameter of 1.75+/-0.05 mm is manufactured under the stretching of a tractor.
Example 2
The 3D printing polypropylene composite material with the high interlayer bonding interface is prepared according to the following method:
(1) Preparing modified inorganic filler: A. will be
Adding the synthesized silicon dioxide with the average sphere diameter of 300nm into toluene, and carrying out ultrasonic treatment to obtain a silicon dioxide suspension; B. under the protection of nitrogen, the silane organic compound (gamma-mercaptopropyl triethoxysilane) is added into the silicon dioxide suspension drop by drop, and the mixture is stirred and reacted for 24 hours at 100 ℃; C. after the reaction was completed, residual γ -mercaptopropyltriethoxysilane was removed by washing with ethanol to obtain silica having thiol groups, and it was dried under vacuum at 25℃for 24 hours.
(2) Uniformly stirring 80 parts of polypropylene (1100N, ningpo), 10 parts of ethylene-methacrylic acid copolymer (EMAA, duPont Nucrel 2940), 10 parts of silicon dioxide containing thiol groups and 0.5 part of antioxidant (a mixture formed by hindered phenol antioxidant 1010 and phosphite antioxidant 168 according to the mass ratio of 1:1), putting into a double screw, uniformly melting and mixing, granulating and drying to obtain polypropylene composite granules;
(3) The polypropylene composite granules are put into a single screw extruder, are melt extruded into a water bath at 40 ℃, and are stretched by a tractor to prepare the 3D printing polypropylene material with the diameter of 1.75+/-0.05 mm.
Example 3
The 3D printing polypropylene composite material with the high interlayer bonding interface is prepared according to the following method:
(1) Preparing modified inorganic filler: A. adding montmorillonite into dimethylbenzene, and carrying out ultrasonic treatment to obtain montmorillonite suspension; B. under the protection of nitrogen, dropwise adding gamma-aminopropyl triethoxysilane into the montmorillonite suspension, and stirring at 100 ℃ for reaction for 24 hours; C. after the reaction was completed, residual γ -aminopropyl triethoxysilane was removed by washing with ethanol to obtain montmorillonite having an amino group, and it was dried under vacuum at 25 ℃ for 24 hours.
(2) Uniformly stirring 70 parts of polypropylene (1100N, ningpo), 20 parts of ethylene-acrylic acid copolymer (EAA), 10 parts of montmorillonite with amino and 0.1 part of antioxidant (a mixture formed by phenol-resistant antioxidant 1010 and phosphite antioxidant 168 according to the mass ratio of 1:1), putting into a double screw, melting and mixing uniformly, granulating and drying to obtain polypropylene composite granules;
(3) The polypropylene composite granules are put into a single screw extruder, are melt extruded into a water bath at 25 ℃, and are stretched by a tractor to prepare the 3D printing polypropylene material with the diameter of 1.75+/-0.05 mm.
Example 4
The 3D printing polypropylene composite material with the high interlayer bonding interface is prepared according to the following method:
1) Preparing modified inorganic filler: A. will be
Adding the synthesized silicon dioxide with the average sphere diameter of 300nm into toluene, and carrying out ultrasonic treatment to obtain a silicon dioxide suspension; B. under the protection of nitrogen, the methacryloxypropyl tris (trimethylsiloxy) silane is added into the silicon dioxide suspension drop by drop, and the mixture is stirred and reacted for 2 hours at 120 ℃; C. after the reaction was completed, the residual methacryloxypropyl tris (trimethylsiloxy) silane was removed by washing with ethanol to give silica bearing acyloxy groups, which was dried under vacuum at 120℃for 2h.
(2) Uniformly stirring 80 parts of polypropylene (1100N, ningpo), 10 parts of ethylene/ethyl acrylate copolymer (EEA), 10 parts of hydroxyl-containing silicon dioxide and 1.0 part of antioxidant (a mixture formed by phenol-blocking antioxidant 1010 and phosphite antioxidant 168 according to the mass ratio of 1:1), putting into a double screw, uniformly melting and mixing, granulating and drying to obtain polypropylene composite granules;
(3) The polypropylene composite granules are put into a single screw extruder, are melt extruded into a water bath at 50 ℃, and are stretched by a tractor to prepare the 3D printing polypropylene material with the diameter of 1.75+/-0.05 mm.
Comparative example 1
The 3D printing polypropylene composite material is prepared according to the following method:
(1) Preparing modified inorganic filler: A. will be
Adding the synthesized silicon dioxide with the average sphere diameter of 300nm into dimethylbenzene, and carrying out ultrasonic treatment to obtain inorganic filler suspension; B. under the protection of nitrogen, dropwise adding dodecyl trimethoxy silane into the silicon dioxide suspension, and stirring at 120 ℃ for reaction for 24 hours; C. after the reaction was completed, the residual silane coupling agent was removed by washing with ethanol to obtain silica having long chain alkyl groups, and vacuum-dried at 25℃for 12 hours.
(2) Uniformly stirring 80 parts of polypropylene (1100N, ningpo), 10 parts of ethylene-methacrylic acid copolymer (EMAA, duPont Nucrel 2940), 10 parts of silicon dioxide with long-chain alkyl and 0.5 part of antioxidant, putting into a double screw, uniformly melting and mixing, granulating and drying to obtain polypropylene composite granules;
(3) The polypropylene composite granules are put into a single screw extruder, are melt extruded into a water bath at 40 ℃, and are stretched by a tractor to prepare the 3D printing polypropylene material with the diameter of 1.75+/-0.05 mm.
Comparative example 2
The 3D printing polypropylene composite material is prepared according to the following method:
(1) Uniformly stirring 90 parts of polypropylene (1100N, ning coal), 10 parts of ethylene-methacrylic acid copolymer (EMAA, duPont Nucrel 2940) and 0.5 part of antioxidant, putting into a double screw, uniformly melting and mixing, granulating and drying to obtain polypropylene composite granules;
(3) The polypropylene composite granules are put into a single screw extruder, are melt extruded into a water bath at 40 ℃, and are stretched by a tractor to prepare the 3D printing polypropylene material with the diameter of 1.75+/-0.05 mm.
Comparative example 3
The 3D printing polypropylene composite material is prepared according to the following method:
(1) 100 parts of polypropylene (1100N, ningpo) and 0.5 part of antioxidant are stirred uniformly, put into a double screw for melting and mixing uniformly, and then granulated and dried to obtain polypropylene composite granules;
(3) The polypropylene composite granules are put into a single screw extruder, are melt extruded into a water bath at 40 ℃, and are stretched by a tractor to prepare the 3D printing polypropylene material with the diameter of 1.75+/-0.05 mm.
Testing of interlayer bonding interfaces
The materials prepared in examples 1-5 and comparative examples 1-3 above were printed with the required a dumbbell tensile bars in ISO527 using a homemade FDM printer, with the fill path set at 90 ° so that the wire alignment direction was perpendicular to the stress loading direction of the tensile bars. And testing the tensile property of the sample bar by a universal testing machine to obtain the bonding strength between the wire bar layers. The nozzle temperature was set at 210℃and the floor temperature was set at 90℃and the printing rate was set at 40mm/s.
Fig. 1 is a mechanism diagram of forming chemical bonds at an interlayer interface of a 3D printed polypropylene material with a high interlayer bonding interface prepared in example 2, wherein the functional filler is the 3D printed polypropylene material with a high interlayer bonding interface prepared in example 2; fig. 2 is a 3D printed article obtained by 3D printing of the polypropylene material prepared in example 2 with high interlayer bonding interface. The tensile strength of the different materials and the interlayer bonding strength of the a-type dumbbell tensile bars printed from the different materials were tested and the results are shown in table 1.
TABLE 1 tensile Strength of different materials and interlayer bond Strength of A-type dumbbell tensile bars printed from different materials
| Tensile Strength (MPa) of Polypropylene composite wire | Interlayer bonding strength (MPa) of 3D printed matter | |
| Example 1 | 32.7 | 30.4 |
| Example 2 | 31.9 | 28.7 |
| Example 3 | 25.7 | 20.1 |
| Example 4 | 30.8 | 22.5 |
| Comparative example 1 | 30.5 | 15.1 |
| Comparative example 2 | 20.7 | 14.2 |
| Comparative example 3 | 38.6 | 13.6 |
As can be seen from fig. 1, fig. 2 and table 1, according to the invention, the prepared 3D printing polypropylene material has good tensile strength by adding the inorganic filler with thiol groups, epoxy groups and amino groups on the surface into the polypropylene and ethylene-acrylic acid copolymer, and the 3D printing part formed by printing the polypropylene material has good interlayer bonding strength.
In summary, the invention discloses a 3D printing polypropylene material with a high interlayer bonding interface, which comprises, by weight, 70-90 parts of polypropylene, 10-20 parts of ethylene-acrylic acid copolymer, 1-10 parts of modified inorganic filler and 0.1-1 part of antioxidant. The 3D printing polypropylene material has the advantages of high interlayer bonding interface strength, good toughness and the like, and is suitable for solving the technical problem of mechanical anisotropy of the existing 3D printing polypropylene.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is intended to be covered by the claims of the present invention.
Claims (9)
1. The 3D printing polypropylene material with the high interlayer bonding interface is characterized by comprising, by weight, 70-90 parts of polypropylene, 10-20 parts of acrylic acid copolymer, 1-10 parts of modified inorganic filler and 0.1-1 part of antioxidant;
the modified inorganic filler is an inorganic filler with any one or more of thiol groups, epoxy groups, amino groups and hydroxyl groups on the surface, wherein the inorganic filler is any one or two of silicon dioxide or montmorillonite;
the antioxidant is any one or more of hindered phenol antioxidants, phosphorous acid antioxidants and alkyl ester antioxidants.
2. The 3D printed polypropylene material according to claim 1, wherein the acid content of the acrylic copolymer is 4-10% and the melt index measured under the test condition of 190 ℃/2.16Kg is 2-15 g/10min.
3. The 3D printed polypropylene material according to claim 2, wherein the acrylic copolymer has a melt index of 5 to 10g/10min tested under test conditions of 190 ℃/2.16 Kg.
4. The 3D printed polypropylene material according to claim 2, wherein the acrylic copolymer is any one or more of an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, an ethylene/ethyl acrylate copolymer or an ethylene vinyl acetate copolymer.
5. The 3D printed polypropylene material according to claim 1, wherein the modified inorganic filler is prepared according to the following method:
A. adding an inorganic filler into a solvent, and performing ultrasonic treatment to obtain an inorganic filler suspension, wherein the solvent is any one or more of toluene, dimethylbenzene, ethanol and water;
B. dropwise adding a silane organic compound into an inorganic filler suspension under the protection of nitrogen, and stirring at 100-120 ℃ for reacting for 2-24 hours, wherein the silane organic compound is any one or more of aminosilane, methacryloxy silane, epoxy silane, mercapto silane or long-chain silane, and the number of carbon atoms on a main chain in the long-chain silane is not less than 10;
C. after the reaction is finished, the residual silane organic compound is removed by ethanol cleaning, and the modified inorganic filler is obtained by vacuum drying for 2 to 24 hours at the temperature of between 25 and 120 ℃.
6. The 3D printed polypropylene material according to claim 5, wherein the mass ratio of the silane coupling agent to the inorganic filler is 1:1 to 3:1.
7. The 3D printed polypropylene material according to claim 1, wherein the modified inorganic filler has an average particle size of 50 to 300nm.
8. The 3D printed polypropylene material according to claim 1, wherein the antioxidant is a mixture of hindered phenolic antioxidant 1010 and phosphite antioxidant 168 in a mass ratio of 1:1.
9. The method for preparing the 3D printing polypropylene material according to any one of claims 1 to 8, wherein the preparation method is specifically as follows:
(1) According to the weight portions, mixing polypropylene, acrylic acid copolymer, modified inorganic filler and antioxidant, stirring uniformly, putting into a double screw, extruding after melting and mixing uniformly, granulating and drying to obtain polypropylene composite granules;
(2) And (3) putting the polypropylene composite granules into a single screw extruder, melting, extruding into a water bath at 25-50 ℃, and extruding filaments to obtain the 3D printing polypropylene material with the high interlayer bonding interface.
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