CN107353627B - TPU/dendritic phthalocyanine loaded SiO with photocatalytic effect2Composite wire and preparation method thereof - Google Patents
TPU/dendritic phthalocyanine loaded SiO with photocatalytic effect2Composite wire and preparation method thereof Download PDFInfo
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- CN107353627B CN107353627B CN201710677907.5A CN201710677907A CN107353627B CN 107353627 B CN107353627 B CN 107353627B CN 201710677907 A CN201710677907 A CN 201710677907A CN 107353627 B CN107353627 B CN 107353627B
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 41
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 11
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 10
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 10
- 238000007493 shaping process Methods 0.000 claims abstract description 9
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- 238000001125 extrusion Methods 0.000 claims abstract description 8
- 239000004014 plasticizer Substances 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 238000010146 3D printing Methods 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- -1 arylene ether Chemical compound 0.000 claims description 13
- 150000008378 aryl ethers Chemical class 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 8
- 239000000347 magnesium hydroxide Substances 0.000 claims description 8
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000004804 winding Methods 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000006731 degradation reaction Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000011550 stock solution Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 4
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 239000000412 dendrimer Substances 0.000 claims 1
- 229920000736 dendritic polymer Polymers 0.000 claims 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 5
- 239000010865 sewage Substances 0.000 abstract description 5
- 239000003570 air Substances 0.000 abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000002689 soil Substances 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005469 granulation Methods 0.000 abstract 1
- 230000003179 granulation Effects 0.000 abstract 1
- 238000005096 rolling process Methods 0.000 abstract 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 48
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 47
- 239000004372 Polyvinyl alcohol Substances 0.000 description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 description 14
- 239000012153 distilled water Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- 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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- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses TPU/dendritic phthalocyanine loaded SiO with a photocatalytic effect2A composite wire and a method for producing the same. The invention provides a TPU/dendritic phthalocyanine loaded SiO with photocatalysis effect by taking high-light-transmission resin TPU as a carrier2A composite wire and a method for producing the same. The technical scheme of the invention is as follows: 1. according to the mass ratio, the formula is that TPU55-75, PVA5-25, 1-3 substituted aryl ether dendritic phthalocyanine complex load SiO25 to 20 portions of plasticizer, 2 to 8 portions of plasticizer, 1 to 5 portions of stabilizer and 0.5 to 2 portions of dispersant. 2. The preparation method comprises the following steps:drying, weighing and mixing; melt extrusion granulation; and (5) extruding, shaping and rolling. The composite wire prepared by the invention has good light transmission and visible light photocatalysis performance, the preparation method is simple and efficient, and the composite wire can be applied to photocatalytic degradation treatment of organic pollutants in sewage, air and soil.
Description
Technical Field
The invention belongs to a TPU/dendritic phthalocyanine loaded SiO with a photocatalytic effect2A composite wire and a method for producing the same.
Background
Chinese patent ZL2014108005249 discloses SiO supported by 1-3 generation aryl ether dendritic phthalocyanine complex2Preparation method and application of visible light photocatalyst, and dendritic phthalocyanine supported SiO in patent2Has the advantages of high active oxygen yield, good hydrophilicity, difficult agglomeration, high electron transfer rate and the like, and can be applied to the fields of industrial sewage treatment, dye wastewater degradation and the like. However, solid powdery dendritic phthalocyanine supported SiO2In practical application, the problems of device formation and recycling exist.
3D prints to be a novel intelligent manufacturing technique, compares traditional shaping mode, and its advantage such as quick preparation, meticulous manufacturing, material utilization rate height are received attentions. Fused Deposition Modeling (FDM) is an important component of 3D printing technology, which can form devices with complex structures from materials stacked through fuses, making the materials device.
TPUs, known by the generic name thermoplastic polyurethane elastomers, are block copolymers composed of soft oligomeric polyol segments and hard diisocyanate segments. The TPU not only has good processing performance, oil resistance, ozone resistance and excellent elasticity, but also is a high-transparency material and has high transparency. At present, TPU resin is mainly applied to the fields of sports goods, packaging materials, textile fabrics, building materials and the like, and reports of direct application to the field of 3D printing are few.
Thus, the dendritic phthalocyanine was SiO-supported2The material is blended with TPU resin, and simultaneously water-soluble polymer polyvinyl alcohol (PVA) is added as a pore-foaming agent to prepare a 3D printing wire rod, so that the dendritic phthalocyanine supported SiO is realized on the basis of combining with FDM technology2The device is formed and applied to photocatalytic degradation treatment of organic pollutants in sewage, air and soil.
Disclosure of Invention
Against the background and problems mentioned above, the object of the present invention is to solve the problem of SiO-supported dendritic phthalocyanine2Has the problems of device formation, recycling and the like, takes high-light-transmission resin TPU as a carrier, and provides TPU/dendritic phthalocyanine loaded SiO with photocatalytic effect2A composite wire and a method for producing the same. The composite wire prepared by the invention has good light transmission and visible light photocatalysis performance, the preparation method is simple and efficient, and the composite wire can be applied to photocatalytic degradation treatment of organic pollutants in sewage, air and soil.
The purpose of the invention is realized by the following technical scheme:
TPU/dendritic phthalocyanine loaded SiO with photocatalytic effect2The composite wire is characterized by being prepared from the following components in percentage by weight:
TPU 55-75
PVA 5-25
SiO supported by 1-3 substituted aryl ether dendritic phthalocyanine complex25-20
2-8 parts of plasticizer
Stabilizer 1-5
0.5-2 parts of dispersing agent.
At least one plasticizer is selected from glycerol, glycol and polyethylene glycol.
At least one stabilizer is selected from calcium hydroxide, calcium oxide and magnesium hydroxide.
At least one dispersant is selected from stearic acid, polyethylene wax and oxidized polyethylene wax.
The TPU/dendritic phthalocyanine supported SiO with the photocatalytic effect2The preparation method of the composite wire is characterized by comprising the following steps:
A. respectively vacuum-drying TPU and a stabilizer, and then loading SiO on the TPU, PVA, a plasticizer, the stabilizer, a dispersant and a 1-3 generation aryl ether dendritic phthalocyanine complex2Accurately weighing according to the weight percentage formula, and then uniformly mixing the weighed components in a high-speed mixer to obtain a mixture;
B. melting and extruding the mixture by a double-screw extruder to obtain blended particles, wherein the charging barrel temperature is 160-220 ℃, and the screw rotating speed is 50-300 rpm/min;
C. and adding the blended particles into a single-screw extruder of a 3D wire production line for extrusion, shaping and winding to obtain the 3D printing wire, wherein the temperature of a charging barrel is 160-220 ℃, and the rotating speed of a screw is 10-100 rpm/min.
The TPU/dendritic phthalocyanine SiO supported with the photocatalytic effect is described above2The application of the composite wire is characterized in that: the TPU/dendritic phthalocyanine carries SiO2The composite wire is applied to the field of 3D printing.
The TPU/dendritic phthalocyanine SiO supported with the photocatalytic effect is described above2The application of the composite wire is characterized in that: the TPU/dendritic phthalocyanine carries SiO2The composite wire is applied to catalytic degradation of phenol.
The invention has the beneficial effects that: 1) the composite wire prepared by the invention is a high polymer material for 3D printing, can be molded and printed at a lower temperature, and has high quality, excellent performance and good light transmission; 2) the composite wire prepared by the invention has good light transmittance and visible light photocatalysis performance, and the preparation method is simple and efficient, and can be applied to photocatalytic degradation treatment of organic pollutants in sewage, air and soil.
Drawings
FIG. 1 shows a TPU/dendritic phthalocyanine supported SiO with photocatalytic effect2And 3D printing a formed product drawing on the composite wire.
FIG. 2 shows a TPU/dendritic phthalocyanine supported SiO with photocatalytic effect2The composite wire 3D printing molded product is subjected to catalytic degradation of phenol activity diagram for multiple times under the condition of visible light.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but it should not be construed that the scope of the present invention is limited to the examples. The examples of the invention used the Desmopan TPU product from Bayer, Germany.
Example 1
1. TPU/dendritic phthalocyanine loaded SiO with photocatalytic effect2The composite wire is characterized by comprising the following components in percentage by weight:
TPU 62
PVA 15
SiO supported by 1-3 substituted aryl ether dendritic phthalocyanine complex212
Glycerol 6
2. The TPU/dendritic phthalocyanine supported SiO with photocatalytic effect2The preparation method of the composite wire comprises the following steps:
A. respectively vacuum-drying TPU and calcium oxide, and then loading SiO on TPU, PVA, glycerol, calcium oxide, stearic acid and 1-3 generation aryl ether dendritic phthalocyanine complex2Accurately weighing according to the weight percentage formula, and then uniformly mixing the weighed components in a high-speed mixer to obtain a mixture;
B. melting and extruding the mixture by a double-screw extruder to obtain blended particles, wherein the temperature of a charging barrel is 160, 170, 180, 185, 190, 195, 200, 195 and 190 ℃ in sequence, and the rotating speed of a screw is 150 rpm/min;
C. adding the blended particles into a single-screw extruder of a 3D wire production line for extrusion, shaping and winding to obtain a 3D printing wire, wherein the temperature of a charging barrel is 175, 185, 195 and 190 ℃ in sequence, and the rotating speed of a screw is 30 rpm/min;
D. printing the wire rod obtained in the step C to obtain TPU/dendritic phthalocyanine loaded SiO2A composite wire 3D printing molded product is specifically shown in FIG. 1;
E. a 500W tungsten halogen lamp is used as a light source (placed in a double-layer glass jacket (through condensed water), the optical filter ensures that the wavelength lambda of incident light is between 420 and 800 nm), and the concentration is 1.35 multiplied by 10 at 250mL-4Adding the product (4.25 g) obtained in the step D into mol/L phenol aqueous solution, carrying out a photocatalytic degradation experiment, and carrying out ultraviolet-visible spectrum analysis on the phenol aqueous solution every hour (the concentration change of the phenol aqueous solution in the degradation process is determined according to the light absorption value at 233 nm of a sample), wherein the total time is 5 hours; the recovered product is repeated twice according to the method to obtain TPU/dendritic phthalocyanine loaded SiO2An activity diagram of a composite wire 3D printed and molded product for catalyzing and degrading phenol for multiple times under a visible light condition is specifically shown in FIG. 2.
Example 2
1. TPU/dendritic phthalocyanine loaded SiO with photocatalytic effect2The composite wire is characterized by comprising the following components in percentage by weight:
TPU 68
PVA 13
SiO supported by 1-3 substituted aryl ether dendritic phthalocyanine complex 210
Calcium oxide 2.8
Polyethylene wax 1.2.
2. The above TPU/dendritic phthalocyanine having photocatalytic effectSiO-loaded substrate2The preparation method of the composite wire comprises the following steps:
A. respectively vacuum-drying TPU and calcium oxide, and then loading SiO on TPU, PVA, ethylene glycol, calcium oxide, polyethylene wax and 1-3 generation aryl ether dendritic phthalocyanine complex2Accurately weighing according to the weight percentage formula, and then uniformly mixing the weighed components in a high-speed mixer to obtain a mixture;
B. melting and extruding the mixture by a double-screw extruder to obtain blended particles, wherein the temperature of a charging barrel is 160, 172, 180, 183, 192, 195, 200, 198, 195 and 192 ℃ in sequence, and the rotating speed of a screw is 180 rpm/min;
C. and adding the blended particles into a single-screw extruder of a 3D wire production line for extrusion, shaping and winding to obtain the 3D printing wire, wherein the cylinder temperature is 172, 184, 195, 197 and 193 ℃ in sequence, and the screw rotation speed is 45 rpm/min.
Example 3
1. TPU/dendritic phthalocyanine loaded SiO with photocatalytic effect2The composite wire is characterized by comprising the following components in percentage by weight:
TPU 60
PVA 15
SiO supported by 1-3 substituted aryl ether dendritic phthalocyanine complex216
Polyethylene glycol 5.5
Polyethylene wax 1.5.
2. The TPU/dendritic phthalocyanine supported SiO with photocatalytic effect2The preparation method of the composite wire comprises the following steps:
A. respectively vacuum-drying TPU and magnesium hydroxide, and then loading SiO on TPU, PVA, polyethylene glycol, magnesium hydroxide, polyethylene wax and 1-3 generation aryl ether dendritic phthalocyanine complex2Accurately weighing according to the weight percentage formula, and then uniformly mixing the weighed components in a high-speed mixer to obtain a mixtureFeeding;
B. melting and extruding the mixture by a double-screw extruder to obtain blended particles, wherein the charging barrel temperature is 163, 175, 180, 183, 190, 195, 203, 198, 196 and 190 ℃ in sequence, and the screw rotating speed is 200 rpm/min;
C. and adding the blended particles into a single-screw extruder of a 3D wire production line for extrusion, shaping and winding to obtain the 3D printing wire, wherein the temperature of a charging barrel is 175, 180, 193, 195 and 195 ℃ in sequence, and the rotating speed of a screw is 25 rpm/min.
Example 4
1. TPU/dendritic phthalocyanine loaded SiO with photocatalytic effect2The composite wire is characterized by comprising the following components in percentage by weight:
TPU 72
SiO supported by 1-3 substituted aryl ether dendritic phthalocyanine complex 210
Magnesium hydroxide 1.5
Oxidized polyethylene wax 1.5.
2. The TPU/dendritic phthalocyanine supported SiO with photocatalytic effect2The preparation method of the composite wire comprises the following steps:
A. respectively vacuum-drying TPU and magnesium hydroxide, and then loading SiO on TPU, PVA, glycerol, magnesium hydroxide, oxidized polyethylene wax and 1-3 generation aryl ether dendritic phthalocyanine complex2Accurately weighing according to the weight percentage formula, and then uniformly mixing the weighed components in a high-speed mixer to obtain a mixture;
B. melting and extruding the mixture by a double-screw extruder to obtain blended particles, wherein the temperature of a charging barrel is 160, 175, 180, 183, 192, 195, 200, 197, 195 and 192 ℃ in sequence, and the rotating speed of a screw is 220 rpm/min;
C. and adding the blended particles into a single-screw extruder of a 3D wire production line for extrusion, shaping and winding to obtain the 3D printing wire, wherein the temperature of a charging barrel is 175, 183, 195, 198 and 195 ℃ in sequence, and the rotating speed of a screw is 36 rpm/min.
Example 5
1. TPU/dendritic phthalocyanine loaded SiO with photocatalytic effect2The composite wire is characterized by comprising the following components in percentage by weight:
TPU 56
PVA 21
SiO supported by 1-3 substituted aryl ether dendritic phthalocyanine complex213
Ethylene glycol 6
2. The TPU/dendritic phthalocyanine supported SiO with photocatalytic effect2The preparation method of the composite wire comprises the following steps:
A. respectively vacuum-drying TPU and calcium hydroxide, and then loading SiO on TPU, PVA, ethylene glycol, calcium hydroxide, stearic acid and 1-3 generation aryl ether dendritic phthalocyanine complex2Accurately weighing according to the weight percentage formula, and then uniformly mixing the weighed components in a high-speed mixer to obtain a mixture;
B. melting and extruding the mixture by a double-screw extruder to obtain blended particles, wherein the temperature of a charging barrel is 160, 172, 183, 185, 190, 195, 198, 195 and 193 ℃ in sequence, and the rotating speed of a screw is 165 rpm/min;
C. and adding the blended particles into a single-screw extruder of a 3D wire production line for extrusion, shaping and winding to obtain the 3D printing wire, wherein the temperature of a charging barrel is 178, 185, 195 and 193 ℃ in sequence, and the rotating speed of a screw is 25 rpm/min.
Note: SiO-Supported by the 1-3 generation arylene ether dendritic phthalocyanine complex used in the above examples 1 to 52SiO is loaded by adopting the invention patent '1-3 generation aryl ether dendritic phthalocyanine complex' previously granted by the inventor2Preparation method of visible light photocatalyst and application thereof (ZL 2014108005249) to prepare obtained product, and specific productThe product is prepared by adopting the preparation method disclosed in the specification with the patent number of 2014108005249, namely any one of the following specific examples 1-3, and the specific steps are as follows:
the 1-3 generation arylene ether dendritic phthalocyanine complex is loaded with SiO2The preparation method of the visible light photocatalyst comprises the following steps:
(1) preparing 50-80 mL of mother liquor containing 70-95% by volume of isopropanol aqueous solution or 70-95% by volume of ethanol aqueous solution;
(2) adding concentrated ammonia water into the solution obtained in the step (1) to adjust the pH value to 7-12, and stirring and uniformly mixing the mixed solution under the water bath condition of 30-70 ℃;
(3) adding 0.2-1.5 ml of N, N-dimethylformamide stock solution of the 1-3 generation aryl ether dendritic phthalocyanine complex with the concentration of 0.001-0.02 mol/L into the solution obtained in the step (2), and stirring and uniformly mixing the solution;
(4) and (4) adding tetraethoxysilane into the solution obtained in the step (3), continuously stirring for 4-12 hours to fully hydrolyze the tetraethoxysilane, and finally filtering, washing and drying the solution at the temperature of 60-110 ℃ to obtain the required catalyst.
The central atom in the 1-3 generation arylene ether dendritic phthalocyanine complex is zinc, copper, cobalt or iron.
Specific example 1
(1) Adding 8 ml of distilled water into 50ml of isopropanol, and uniformly stirring under the water bath condition of 65 ℃;
(2) adding 1 ml of concentrated ammonia water and 1 ml of stock solution (0.02 mol/L) of 1-3 substituted aryl ether dendritic phthalocyanine complex (zinc as central atom) into the mixed solution, and continuing stirring for 5 min;
(3) adding 8 mL of tetraethoxysilane into the solution, continuously stirring for 12 h to fully hydrolyze the mixture, finally filtering the solution, washing (10 mL for 3 times of isopropanol washing and 10 mL for 5 times of distilled water washing), drying the solid at 70 ℃ to obtain the required 1-3 generation arylene ether dendritic phthalocyanine complex (the central atom is zinc) loaded with SiO2A catalyst.
Specific example 2
(1) Adding 10 ml of distilled water into 50ml of absolute ethyl alcohol, and uniformly stirring under the water bath condition of 65 ℃;
(2) adding 1 ml of concentrated ammonia water and 0.5 ml of stock solution (0.01 mol/L) of 1-3 substituted aryl ether dendritic phthalocyanine complex (zinc as central atom) into the mixed solution, and continuing stirring for 5 min;
(3) adding 8 mL of tetraethoxysilane into the solution, continuously stirring for 8 h to fully hydrolyze the mixture, finally filtering the solution, washing (10 mL for 3 times of isopropanol washing and 10 mL for 5 times of distilled water washing), drying the solid at 70 ℃ to obtain the required 1-3 generation arylene ether dendritic phthalocyanine complex (the central atom is zinc) loaded with SiO2A catalyst.
Specific example 3
(1) Adding 8 ml of distilled water into 50ml of isopropanol, and uniformly stirring under the water bath condition of 65 ℃;
(2) adding 0.46 ml of concentrated ammonia water and 1 ml of stock solution (0.02 mol/L) of 1-3 substituted aryl ether dendritic phthalocyanine complex (zinc as central atom) into the mixed solution, and continuously stirring for 5 min;
(3) adding 8 mL of tetraethoxysilane into the solution, continuing stirring for 12 hours to fully hydrolyze the mixture, finally filtering the solution, washing (3 times of isopropanol washing and 10 mL of distilled water washing), and drying the solid at 70 ℃ to obtain the required catalyst.
The above-described embodiments are further detailed descriptions of the present invention, but the scope of the claims of the present invention is not limited to the scope described in the embodiments, and all technical solutions using equivalent substitutions or equivalent modifications fall within the scope of the claims of the present invention.
Claims (7)
1. TPU/dendritic phthalocyanine loaded SiO with photocatalytic effect2The composite wire is characterized by being prepared from the following components in percentage by weight:
TPU 55-75
PVA 5-25
SiO supported by 1-3 substituted aryl ether dendritic phthalocyanine complex25-20
2-8 parts of plasticizer
Stabilizer 1-5
0.5-2 parts of dispersant
SiO supported by the 1-3 generation aryl ether dendritic phthalocyanine complex2Prepared by the following method, which comprises the following steps:
(1) preparing 50-80 mL of mother liquor containing 70-95% by volume of isopropanol aqueous solution or 70-95% by volume of ethanol aqueous solution;
(2) adding concentrated ammonia water into the solution obtained in the step (1) to adjust the pH value to 7-12, and stirring and uniformly mixing the mixed solution under the water bath condition of 30-70 ℃;
(3) adding 0.2-1.5 ml of N, N-dimethylformamide stock solution of the 1-3 generation aryl ether dendritic phthalocyanine complex with the concentration of 0.001-0.02 mol/L into the solution obtained in the step (2), and stirring and uniformly mixing the solution;
(4) adding tetraethoxysilane into the solution obtained in the step (3), continuously stirring for 4-12 hours to fully hydrolyze the tetraethoxysilane, and finally filtering, washing and drying the solution at the temperature of 60-110 ℃ to obtain the required catalyst;
the central atom in the 1-3 generation arylene ether dendritic phthalocyanine complex is zinc, copper, cobalt or iron.
2. The TPU/dendritic phthalocyanine SiO supported photocatalytic effect as claimed in claim 12The composite wire is characterized in that at least one plasticizer is selected from glycerol, glycol and polyethylene glycol.
3. The TPU/dendritic phthalocyanine SiO supported photocatalytic effect as claimed in claim 12The composite wire is characterized in that at least one stabilizer is selected from calcium hydroxide, calcium oxide,And (3) magnesium hydroxide.
4. The TPU/dendritic phthalocyanine SiO supported photocatalytic effect as claimed in claim 12The composite wire is characterized in that at least one dispersing agent is selected from stearic acid, polyethylene wax and oxidized polyethylene wax.
5. TPU/dendrimer phthalocyanine SiO-supported photocatalytic effect according to claims 1 to 42The preparation method of the composite wire is characterized by comprising the following steps:
A. respectively vacuum-drying TPU and a stabilizer, and then loading SiO on the TPU, PVA, a plasticizer, the stabilizer, a dispersant and a 1-3 generation aryl ether dendritic phthalocyanine complex2Accurately weighing according to the weight percentage formula, and then uniformly mixing the weighed components in a high-speed mixer to obtain a mixture;
B. melting and extruding the mixture by a double-screw extruder to obtain blended particles, wherein the charging barrel temperature is 160-220 ℃, and the screw rotating speed is 50-300 rpm/min;
C. and adding the blended particles into a single-screw extruder of a 3D wire production line for extrusion, shaping and winding to obtain the 3D printing wire, wherein the temperature of a charging barrel is 160-220 ℃, and the rotating speed of a screw is 10-100 rpm/min.
6. TPU/dendritic phthalocyanine SiO supported photocatalytic effect according to any of claims 1 to 42Composite wire or TPU/dendritic phthalocyanine SiO-supported wire produced by the process according to claim 52The application of the composite wire is characterized in that: the TPU/dendritic phthalocyanine carries SiO2The composite wire is applied to the field of 3D printing.
7. TPU/dendritic phthalocyanine SiO supported photocatalytic effect according to any of claims 1 to 42Composite wire or TPU/dendritic phthalocyanine SiO-supported wire produced by the process according to claim 52The application of the composite wire is characterized in that: the above-mentionedTPU/dendritic phthalocyanine SiO-supported2The composite wire is applied to catalytic degradation of phenol.
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| CN112138722B (en) * | 2020-09-24 | 2022-11-01 | 福建师范大学 | Triphenylamine-based dendritic ligand substituted silicon phthalocyanine loaded SiO2Method for preparing photocatalyst |
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