CN109174203B - Skin-core structure 3D printing wire with photocatalysis function and preparation method thereof - Google Patents
Skin-core structure 3D printing wire with photocatalysis function and preparation method thereof Download PDFInfo
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- CN109174203B CN109174203B CN201810741379.XA CN201810741379A CN109174203B CN 109174203 B CN109174203 B CN 109174203B CN 201810741379 A CN201810741379 A CN 201810741379A CN 109174203 B CN109174203 B CN 109174203B
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- 238000010146 3D printing Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000007146 photocatalysis Methods 0.000 title claims description 10
- 239000011941 photocatalyst Substances 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 229920005570 flexible polymer Polymers 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 13
- 239000012792 core layer Substances 0.000 claims abstract description 5
- 239000004626 polylactic acid Substances 0.000 claims description 25
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 12
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 9
- -1 titanium alkoxide Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 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 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 6
- 238000001782 photodegradation Methods 0.000 claims description 6
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 6
- 229940043267 rhodamine b Drugs 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 239000010445 mica Substances 0.000 claims description 5
- 229910052618 mica group Inorganic materials 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical group [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 2
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- 238000002844 melting Methods 0.000 abstract description 3
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- 239000011162 core material Substances 0.000 description 39
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 12
- 229920006124 polyolefin elastomer Polymers 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 238000007639 printing Methods 0.000 description 5
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- 238000001179 sorption measurement Methods 0.000 description 4
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
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- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000003622 immobilized catalyst Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 229910052721 tungsten Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention discloses a skin-core structure 3D printing wire with a photocatalytic function and a preparation method thereof, wherein the skin-core structure 3D printing wire is prepared by the following steps: (1) preparing a composite photocatalyst; (2) melting and blending the composite photocatalyst and the flexible polymer double screw; (3) the photocatalytic master batch and the PLA single screw are blended and extruded to prepare the wire. The 3D printing wire obtained by the invention has a skin-core structure, the flexible polymer is a skin layer, the PLA is a core layer, the photocatalyst is mainly dispersed in the skin layer, and the photocatalyst is immobilized on the surface of a device in a high orientation manner through deposition melting (FDM), so that the device is realized, the preparation method is simple and efficient, and the preparation method can be applied to photocatalytic degradation treatment of organic pollutants in sewage, air and soil.
Description
Technical Field
The invention belongs to a skin-core structure 3D printing wire with a photocatalytic function and a preparation method thereof.
Background
TiO2Is a typical photocatalyst and has excellent physical and chemical properties such as no toxicity, low price, easy obtaining, stable chemical property, high photocatalytic activity and the like, so the TiO is2And the derivative thereof becomes a hot photocatalyst. Through the diligent research of researchers in recent years, TiO2The photoresponse range and the photocatalytic efficiency of the similar catalyst are continuously improved, and the similar catalyst is widely applied to the fields of photocatalytic water splitting, photodegradation of pollutants, solar cells and the like. However, the difficulty of recycling is always a great difficulty in limiting the application of the catalystHowever, the device is a feasible method for solving the problem.
At present, a plurality of device methods are realized, for example, a catalyst is coated on the surface of various materials, the method has high loading rate but is complex, and the immobilized catalyst is easy to fall off. The method is simple, but most of the catalyst is coated in the polymer, which causes waste.
3D prints to be a neotype intelligent manufacturing technique, compares traditional shaping mode and compares, has advantages such as quick preparation, manufacturing, material utilization rate are high more meticulous. The 3D printing technology which is the most popular Fused Deposition Modeling (FDM) can print high molecular materials into devices with complex structures.
The selected matrix polylactic acid (PLA) is a renewable, degradable and pollution-free environment-friendly material and is also the mainstream material for 3D printing (FDM). The flexible polymer selected is a multi-stage mosaic with excellent elasticity, heat resistance and processability. The invention realizes the sheath-core structure 3D printing wire by process design by utilizing incompatibility of two materials of PLA and flexible polymer (olefin block copolymer (OBCs), polyolefin elastomer (POE) and ethylene-vinyl acetate copolymer (EVA)) and larger density difference (such as OBC: 0.877kg/L and PLA: 1.20-1.30 kg/L). During processing, the two materials are incompatible and can cause severe phase separation, and because the flexible polymer has lower density and better flow rate than PLA at higher temperature, the flexible polymer can be positioned at the outer layer of the melt, and the PLA is positioned at the inner layer of the melt; this "balance" is not disturbed due to the low shear of the single screw. The extruded filaments are therefore in a sheath-core configuration, with the configuration being best at the PLA/flexible polymer (60/40) ratio. The general formula of the silane coupling agent is RSiX3, wherein R represents amino, sulfydryl, vinyl, epoxy, cyano, methacryloxy and other groups, the groups have strong reactivity with different matrix resins, and X represents hydrolyzable alkoxy (such as methoxy, ethoxy and the like). According to the invention, through selecting a proper coupling agent, the affinity of the catalyst and the flexible polymer is improved, the catalyst can be well dispersed in the flexible polymer base material, and the excessive dispersion in PLA can be avoided. Most of the finally prepared 3D printing wire photocatalyst is dispersed in the flexible polymer skin layer. The filament that comes out through printing the nozzle after 3D printing wire rod melting is also skin-core structure. Therefore, the invention can prepare a complex device with the photocatalyst distributed on the surface.
The invention adopts 3D printing technology, which is beneficial to anisotropic distribution of the flake powder for loading the photocatalyst, and high orientation is beneficial to improving the photocatalytic efficiency. This is because the direction of the packing is mainly along the flow direction, and when it hits the blocking force (such as the mold wall, etc.), its flow is changed to be perpendicular to the blocking force. Adding TiO into the mixture2Loaded on flaky powder and can avoid TiO from being used2The particle size is too fine and is coated in a large amount in the matrix resin.
Chinese invention patents CN201610631405.4 and CN201710447874.5 disclose two sheath-core structure wires, both of which are extruded through multiple runners, and have certain requirements on equipment. The invention combines the formula optimization and the process conditions, can be realized by only one screw, is simpler in comparison, and small segments in the blending process are mutually permeated, so that the toughness of the core layer is increased, the strength of the skin layer is increased, and the bonding force of the interface of the two phase layers is stronger.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a skin-core structure 3D printing wire with a photocatalytic function and a preparation method thereof.
In order to realize the invention, the specific technical scheme is as follows:
a skin-core structure 3D printing wire with a photocatalysis function is characterized by comprising the following components in percentage by weight:
P LA 45~70
flexible polymers 29-50
0.5-10% of composite photocatalyst.
The flexible polymer is selected from one or more of OBCs, POE and EVA.
The composite photocatalystPrepared by the following method: stirring and hydrolyzing the flaky powder and titanium alkoxide, wherein the adding amount of the flaky powder is 0.1-10% of the mass of the titanium alkoxide, and preparing the flaky powder/TiO through adjusting the pH2Sol, and mixing the sheet powder/TiO2Drying the sol mixture to a gel state, calcining for 1-5 h to obtain powder, adding the powder and a coupling agent into a high-speed mixer according to a mass ratio of 100: 0.5-2, keeping a rotating speed of 600-2000 rpm, and stirring at a high speed for 5-30 min to obtain the composite photocatalyst, wherein the titanium alkoxide is tetrabutyl titanate, tetraisopropyl titanate or tetraethyl titanate, the flaky powder is one or more of mica, talcum powder, montmorillonite, alumina and barium sulfate, and the coupling agent is a vinyl silane coupling agent.
A preparation method of a skin-core structure 3D printing wire with a photocatalytic function comprises the following steps:
(1) uniformly mixing the composite photocatalyst and the flexible polymer according to the proportion, adding the mixture into a double-screw extruder for melt blending, and extruding and granulating to obtain a photocatalytic master batch;
(2) and (2) uniformly mixing the photocatalytic master batch obtained in the step (1) with PLA (polylactic acid) according to the proportion, adding the mixture into a single-screw extruder for processing, cooling extruded filaments by water, and drawing and controlling the diameter of the filament outlet by a tractor to obtain the skin-core structure 3D printing wire with the photocatalytic function.
The preparation method of the skin-core structure 3D printing wire with the photocatalytic function is characterized in that the radius ratio of a core layer of the wire to the wire is 0.2-0.8: 1.
The preparation method of the skin-core structure 3D printing wire with the photocatalytic function is characterized in that the calcination is performed by adopting a muffle furnace, the heating rate is 5 ℃/min, and the calcination temperature is 200-500 ℃;
the preparation method of the skin-core structure 3D printing wire with the photocatalytic function is characterized in that the parameters of the double-screw extruder are as follows: the first zone is 70-80 ℃, the second zone is 80-90 ℃, the third zone is 90-100 ℃, the fourth zone is 100-;
the preparation method of the skin-core structure 3D printing wire with the photocatalytic function is characterized in that the parameters of the single-screw extruder are as follows: the first zone is 170-;
the 3D printing wire with the skin-core structure and the photocatalytic function, which is prepared by the preparation method, is used for photodegradation of rhodamine B.
After the technical scheme is adopted, the invention has the following characteristics and advantages: 1. the preparation method is simple and efficient, and can be used for preparing complex photocatalytic devices; 2. the percolation threshold of the photocatalyst is reduced, and the photocatalyst is mainly distributed on the surface of the device in a high orientation manner; 3. although the texture of PLA is crisp, the PLA is wrapped by a layer of flexible polymer elastomer, so that the structure of a 3D device is protected; 4. the PLA degradable material is used as the core material to reduce the environmental pollution, the flexible polymer is used as the cortex layer to coat the PLA core material to slow down the degradation of the PLA and prolong the service life of the photocatalytic device.
Drawings
Fig. 1 is an enlarged view of the skin-core peeling of a 3D printing wire with a photocatalytic effect and a skin-core structure prepared by applying example 1 of the present invention.
Fig. 2 is a diagram of a 3D printing wire printing molded product having a photocatalytic effect and a sheath-core structure prepared by applying embodiment 1 of the present invention.
Fig. 3 is a photo-degradation and dark adsorption activity spectrogram of rhodamine B of a 3D printing wire printing molded product with a photocatalytic effect and a skin-core structure prepared in example 1 of the present invention.
Detailed Description
Example 1
A skin-core structure 3D printing wire with a photocatalytic function comprises 45 parts of OBC, 50 parts of PLA and 5 parts of a composite photocatalyst.
The preparation method comprises the following steps:
(1) adding 500 g of talcum powder into 5.0 kg of n-butyl titanate, stirring and hydrolyzing, and adjusting pH =6 by adding hydrochloric acid solution with pH =2 to obtain TiO2A talc powder sol. Then adding TiO2Drying talcum powder sol to a gel state, calcining for 3 h at 500 ℃, adding the obtained powder and 5 g of vinyl triethoxysilane coupling agent (WD-20) into a high-speed mixer, keeping the rotating speed at 2000 rpm, and stirring at a high speed for 30min to obtain the composite photocatalyst;
(2) 0.5 kg of composite photocatalyst and 4.5 kg of OBC are uniformly mixed and then added into a double-screw extruder for melt blending, wherein the parameters of the double-screw extruder are as follows: extruding and granulating at the first zone of 80 ℃, the second zone of 90 ℃, the third zone of 100 ℃, the fourth zone of 110 ℃, the fifth zone of 120 ℃, the sixth zone of 130 ℃, the seventh zone of 130 ℃, the eighth zone of 120 ℃, the ninth zone of 110 ℃, the die head of 100 ℃ at the rotating speed of 200 rpm to obtain photocatalytic OBC master batches;
(3) 5.0 kg of photocatalytic OBC master batch and 5.0 kg of PLA are uniformly mixed and then added into a single-screw extruder for processing, and the parameters of the single-screw extruder are as follows: and the first zone is 170 ℃, the second zone is 180 ℃, the third zone is 190 ℃, the fourth zone is 170 ℃, the rotating speed is 40 rpm, the extruded filament is cooled by water, and the filament diameter is drawn and controlled by a traction machine to obtain the skin-core structure 3D printing wire with the photocatalysis function.
The 3D printing wire with the skin-core structure and the photocatalytic function is printed into a hollow small square through a 3D printer (FDM), specifically, as shown in fig. 1 and fig. 2, fig. 1 is an enlarged peel view of a skin-core of the 3D printing wire with the photocatalytic effect and the skin-core structure prepared by applying embodiment 1 of the present invention, and has an obvious skin layer and core layer, and fig. 2 is a diagram of a printed product of the 3D printing wire with the photocatalytic effect and the skin-core structure prepared by applying embodiment 1 of the present invention.
Adding 4.5 g of the obtained hollow small square blocks with the photocatalytic effect and the skin-core structure into 80 mL of rhodamine B solution with the concentration of 30 mg/L, stirring in the dark for 60 min to achieve adsorption and desorption balance, illuminating by using a visible halogen tungsten lamp (500W) as a light source, sampling at regular intervals, carrying out centrifugal separation, taking supernatant, and respectively measuring absorbance by using an ultraviolet spectrophotometer. The photo-degradation and dark adsorption activity spectrogram (pollutant: 80 mL hollow small square catalyst dosage: 0.22 g) of the 3D printing wire printing and forming product with the photocatalytic effect and the skin-core structure, which is prepared by the embodiment 1 of the invention, on rhodamine B is obtained, and as shown in the figure 3, the 3D printing wire printing and forming product has good photo-degradation and dark adsorption capacity on rhodamine B.
Example 2
A skin-core structure 3D printing wire with a photocatalytic function comprises 45 parts of OBC, 50 parts of PLA and 5 parts of a composite photocatalyst.
The preparation method comprises the following steps:
(1) adding 500 g of montmorillonite into 10.0 kg of n-butyl titanate, stirring and hydrolyzing, and adjusting pH =6 by adding hydrochloric acid solution with pH =2 to obtain TiO2Montmorillonite sol. Then adding TiO2Drying montmorillonite sol to gel state, calcining at 400 ℃ for 5 h, adding the obtained powder and 4 g of vinyltriethoxysilane (A151) into a high-speed mixer, keeping the rotating speed at 2000 rpm, and stirring at high speed for 30min to obtain the composite photocatalyst;
(2) 0.5 kg of composite photocatalyst and 4.5 kg of OBC are uniformly mixed and then added into a double-screw extruder for melt blending, wherein the parameters of the double-screw extruder are as follows: extruding and granulating at the first zone of 80 ℃, the second zone of 90 ℃, the third zone of 100 ℃, the fourth zone of 110 ℃, the fifth zone of 120 ℃, the sixth zone of 130 ℃, the seventh zone of 130 ℃, the eighth zone of 120 ℃, the ninth zone of 110 ℃, the die head of 100 ℃ at the rotating speed of 200 rpm to obtain photocatalytic OBC master batches;
(3) 5.0 kg of photocatalytic OBC master batch and 5.0 kg of PLA are uniformly mixed and then added into a single-screw extruder for processing, and the parameters of the single-screw extruder are as follows: and the first zone is 170 ℃, the second zone is 180 ℃, the third zone is 190 ℃, the fourth zone is 170 ℃, the rotating speed is 40 rpm, the extruded filament is cooled by water, and the filament diameter is drawn and controlled by a traction machine to obtain the skin-core structure 3D printing wire with the photocatalysis function.
Example 3
A skin-core structure 3D printing wire with a photocatalytic function comprises 30 parts of POE, 65 parts of PLA and 5 parts of a composite photocatalyst.
The preparation method comprises the following steps:
(1) adding 500 g of talcum powder into 5.0 kg of n-butyl titanate, stirring and hydrolyzing, and adjusting pH =6 by adding hydrochloric acid solution with pH =2 to obtain TiO2A talc powder sol. Then adding TiO2Talc powderDrying the sol to a gel state, calcining at 500 ℃ for 3 h, adding the obtained powder and 3 g of vinyl trimethoxy silane (A171) into a high-speed mixer, keeping the rotating speed at 2000 rpm, and stirring at high speed for 30min to obtain the composite photocatalyst;
(2) 0.5 kg of composite photocatalyst and 3.0 kg of POE are uniformly mixed and then added into a double-screw extruder for melt blending, wherein the parameters of the double-screw extruder are as follows: extruding and granulating at 75 ℃ in the first zone, 85 ℃ in the second zone, 95 ℃ in the third zone, 100 ℃ in the fourth zone, 115 ℃ in the fifth zone, 125 ℃ in the sixth zone, 125 ℃ in the seventh zone, 115 ℃ in the eighth zone, 105 ℃ in the ninth zone and 100 ℃ in a die head at the rotating speed of 180 rpm to obtain the photocatalytic POE master batch;
(3) 3.5 kg of photocatalytic POE master batch and 6.5 kg of PLA are uniformly mixed and then added into a single-screw extruder for processing, and the parameters of the single-screw extruder are as follows: and the first area is 175 ℃, the second area is 185 ℃, the third area is 195 ℃, the fourth area is 175 ℃, the rotating speed is 30 rpm, the extruded filaments are cooled by water, and the drawn filaments are drawn by a tractor and the diameter of the drawn filaments is controlled to obtain the skin-core structure 3D printing wire with the photocatalysis function.
Example 4
A skin-core structure 3D printing wire with a photocatalytic function comprises 30 parts of POE, 65 parts of PLA and 5 parts of a composite photocatalyst.
The preparation method comprises the following steps:
(1) adding 500 g mica into 5.0 kg n-butyl titanate, stirring for hydrolysis, and adjusting pH =6 by adding hydrochloric acid solution with pH =2 to obtain TiO2Mica sol. Then adding TiO2Drying the mica sol to a gel state, calcining for 3 h at 500 ℃, adding the obtained powder and 6 g of vinyl tri (beta-methoxyethoxy) silane (A172) into a high-speed mixer, keeping the rotating speed at 2000 rpm, and stirring at a high speed for 30min to obtain the composite photocatalyst;
(2) 0.5 kg of composite photocatalyst and 3.0 kg of POE are uniformly mixed and then added into a double-screw extruder for melt blending, wherein the parameters of the double-screw extruder are as follows: extruding and granulating at 75 ℃ in the first zone, 85 ℃ in the second zone, 95 ℃ in the third zone, 100 ℃ in the fourth zone, 115 ℃ in the fifth zone, 125 ℃ in the sixth zone, 125 ℃ in the seventh zone, 115 ℃ in the eighth zone, 105 ℃ in the ninth zone and 100 ℃ in a die head at the rotating speed of 180 rpm to obtain the photocatalytic POE master batch;
(3) 3.5 kg of photocatalytic POE master batch and 6.5 kg of PLA are uniformly mixed and then added into a single-screw extruder for processing, and the parameters of the single-screw extruder are as follows: and the first area is 175 ℃, the second area is 185 ℃, the third area is 195 ℃, the fourth area is 175 ℃, the rotating speed is 30 rpm, the extruded filaments are cooled by water, and the drawn filaments are drawn by a tractor and the diameter of the drawn filaments is controlled to obtain the skin-core structure 3D printing wire with the photocatalysis function.
Example 5
A skin-core structure 3D printing wire with a photocatalytic function is composed of 30 parts of EVA (ethylene vinyl acetate), 69 parts of PLA (polylactic acid) and 1 part of a composite photocatalyst.
The preparation method comprises the following steps:
(1) adding 500 g of alumina to 5.0 kg of n-butyl titanate, stirring for hydrolysis, and adjusting pH =6 by adding hydrochloric acid solution with pH =2 to obtain TiO2Alumina sol. Then adding TiO2Drying the alumina sol to a gel state, calcining for 3 hours at 500 ℃, adding the obtained powder and 5 g of vinyl tri (beta-methoxyethoxy) silane (A172) into a high-speed mixer, keeping the rotating speed at 2000 rpm, and stirring at a high speed for 30 minutes to obtain the composite photocatalyst;
(2) 0.1 kg of composite photocatalyst and 3.0 kg of EVA are uniformly mixed and then added into a double-screw extruder for melt blending, wherein the parameters of the double-screw extruder are as follows: extruding and granulating at 75 ℃ in the first zone, 85 ℃ in the second zone, 95 ℃ in the third zone, 100 ℃ in the fourth zone, 115 ℃ in the fifth zone, 125 ℃ in the sixth zone, 125 ℃ in the seventh zone, 115 ℃ in the eighth zone, 105 ℃ in the ninth zone and 100 ℃ in a die head at the rotating speed of 180 rpm to obtain photocatalytic EVA master batches;
(3) 3.1 kg of photocatalytic EVA master batch and 6.9 kg of PLA are uniformly mixed and then added into a single-screw extruder for processing, and the parameters of the single-screw extruder are as follows: and the first area is 175 ℃, the second area is 185 ℃, the third area is 195 ℃, the fourth area is 175 ℃, the rotating speed is 30 rpm, the extruded filaments are cooled by water, and the drawn filaments are drawn by a tractor and the diameter of the drawn filaments is controlled to obtain the skin-core structure 3D printing wire with the photocatalysis function.
Example 6
A skin-core structure 3D printing wire with a photocatalytic function is composed of 40 parts of EVA (ethylene vinyl acetate), 58 parts of PLA (polylactic acid) and 2 parts of a composite photocatalyst.
The preparation method comprises the following steps:
(1) adding 500 g barium sulfate into 5.0 kg of n-butyl titanate, stirring for hydrolysis, and adjusting pH =6 by adding hydrochloric acid solution with pH =2 to obtain TiO2Barium sulfate sol. Then adding TiO2Drying the barium sulfate sol to a gel state, calcining for 3 hours at 500 ℃, adding the obtained powder and 5 g of vinyl tri (beta-methoxyethoxy) silane (A172)) into a high-speed mixer, keeping the rotating speed at 2000 rpm, and stirring at a high speed for 30 minutes to obtain the composite photocatalyst;
(2) 0.2 kg of composite photocatalyst and 4.0 kg of EVA are uniformly mixed and then added into a double-screw extruder for melt blending, wherein the parameters of the double-screw extruder are as follows: extruding and granulating at 75 ℃ in the first zone, 85 ℃ in the second zone, 95 ℃ in the third zone, 100 ℃ in the fourth zone, 115 ℃ in the fifth zone, 125 ℃ in the sixth zone, 125 ℃ in the seventh zone, 115 ℃ in the eighth zone, 105 ℃ in the ninth zone and 100 ℃ in a die head at the rotating speed of 180 rpm to obtain photocatalytic EVA master batches;
(3) uniformly mixing 4.2 kg of photocatalytic EVA master batch and 5.8 kg of PLA, and adding the mixture into a single-screw extruder for processing, wherein the parameters of the single-screw extruder are as follows: and the first area is 175 ℃, the second area is 185 ℃, the third area is 195 ℃, the fourth area is 175 ℃, the rotating speed is 30 rpm, the extruded filaments are cooled by water, and the drawn filaments are drawn by a tractor and the diameter of the drawn filaments is controlled to obtain the skin-core structure 3D printing wire with the photocatalysis function.
Claims (6)
1. A skin-core structure 3D printing wire with a photocatalysis function is characterized by comprising the following components in percentage by weight:
PLA 45~70
flexible polymers 29-50
0.5-10% of a composite photocatalyst;
the preparation method of the skin-core structure 3D printing wire with the photocatalytic function comprises the following steps:
(1) uniformly mixing the composite photocatalyst and the flexible polymer according to the proportion, adding the mixture into a double-screw extruder for melt blending, and extruding and granulating to obtain a photocatalytic master batch;
(2) uniformly mixing the photocatalytic master batch obtained in the step (1) with PLA (polylactic acid) according to a ratio, adding the mixture into a single-screw extruder for processing, cooling extruded filaments with water, and drawing and controlling the diameter of the filament outlet by a tractor to obtain a skin-core structure 3D printing wire with a photocatalytic function;
the flexible polymer is selected from one or more of OBCs, POE and EVA;
the composite photocatalyst is prepared by the following method: stirring and hydrolyzing the flaky powder and titanium alkoxide, wherein the adding amount of the flaky powder is 0.1-10% of the mass of the titanium alkoxide, and preparing the flaky powder/TiO through adjusting the pH2Sol, and mixing the sheet powder/TiO2Drying the sol mixture to a gel state, calcining for 1-5 h to obtain powder, adding the powder and a coupling agent into a high-speed mixer according to a mass ratio of 100: 0.5-2, keeping a rotating speed of 600-2000 rpm, and stirring at a high speed for 5-30 min to obtain the composite photocatalyst, wherein the titanium alkoxide is tetrabutyl titanate, tetraisopropyl titanate or tetraethyl titanate, the flaky powder is one or more of mica, talcum powder, montmorillonite, alumina and barium sulfate, and the coupling agent is a vinyl silane coupling agent.
2. The skin-core structure 3D printing wire with the photocatalytic function as claimed in claim 1, wherein the ratio of the core layer to the wire radius of the wire is 0.2-0.8: 1.
3. The 3D printing wire rod with the skin-core structure and the photocatalytic function according to claim 1, wherein the calcining is performed in a muffle furnace, the heating rate is 5 ℃/min, and the calcining temperature is 200-500 ℃.
4. The skin-core structured 3D printing wire with the photocatalytic function as claimed in claim 1, wherein the parameters of the twin-screw extruder are as follows: the first zone is 70-80 ℃, the second zone is 80-90 ℃, the third zone is 90-100 ℃, the fourth zone is 100-.
5. The skin-core structured 3D printing wire with the photocatalytic function as claimed in claim 1, wherein the single screw extruder parameters are: the first zone 170-.
6. The core-sheath structure 3D printing wire with the photocatalytic function, according to claim 1, is used for photodegradation of rhodamine B.
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| CN110394193B (en) * | 2019-07-20 | 2022-07-12 | 福建师范大学 | Preparation method of photocatalyst for 3D printing of framework bismuth tungstate |
| CN110697954B (en) * | 2019-09-29 | 2021-04-30 | 华南农业大学 | Photocatalytic degradation device for water treatment and preparation method thereof |
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| CN113980438B (en) * | 2021-09-29 | 2023-02-28 | 淮阴工学院 | Degradable and recyclable 3D printing micropore photocatalytic composite material and preparation method thereof |
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