CN109880313A - A kind of dendritic phthalocyanine@SiO2Water disposal device and preparation method thereof - Google Patents
A kind of dendritic phthalocyanine@SiO2Water disposal device and preparation method thereof Download PDFInfo
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- CN109880313A CN109880313A CN201910110330.9A CN201910110330A CN109880313A CN 109880313 A CN109880313 A CN 109880313A CN 201910110330 A CN201910110330 A CN 201910110330A CN 109880313 A CN109880313 A CN 109880313A
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Abstract
The present invention discloses a kind of dendritic phthalocyanine@SiO2Water disposal device and preparation method thereof, the water disposal device are calculated as 73 ~ 84 parts of high light transmission resin by weight, and PVA coats dendritic phthalocyanine SiO215 ~ 25 parts, 0.5 ~ 2 part of dispersing agent, 0.2 ~ 0.3 part of nucleating agent.The preparation method comprises the following steps: PVA coats dendritic phthalocyanine@SiO2；Dry weighing mixing；Melting extrusion is granulated；Extrusioning shaping winding；3D printing.Water disposal device produced by the present invention has good translucency and visible light photocatalysis performance, and preparation method is simple and efficient, and can be applied to the photocatalytic degradation processing of dirty organic pollutants.
Description
Technical field
The invention belongs to environmental treatment technical fields, and in particular to a kind of dendritic phthalocyanine@SiO2Water disposal device and its
Preparation method.
Background technique
As process of industrialization accelerates, energy shortage and problem of environmental pollution become increasingly conspicuous.Water pollution is always one
Serious environmental problem, even micro heavy, dyestuff, drug are all great to human body damage in water body.At water pollution
There are many reason method, and wherein photocatalysis technology is a kind of effective ways that problem of environmental pollution is solved using new energy, it is utilized
Photocatalytic degradation poisonous and harmful substance provides a kind of very environment protection treating pollution method.But current most of photochemical catalyst
For powder, hardly possible recycling becomes a great problem for limiting its application, and device is then the feasible method for solving this problem.
Chinese patent ZL2014108005249 discloses a kind of 1-3 and loads SiO for aryl oxide dendritic phthalocyanine complex2It can
The preparation method and applications of light-exposed photochemical catalyst, dendritic phthalocyanine described in patent load SiO2Active oxygen yield
The advantages that height, good hydrophilic property, high not easy to reunite and electronics transfer rate, it can be applied to Industrial Waste Water Treatments, degradation of dye waste water etc.
Field.But the dendritic phthalocyanine of solid-state powdery loads SiO2There are problems that device and recycling in practical applications
At present realize device method it is very much, such as by catalyst be coated in a variety of materials surface, CN201510118618.2 with
CN201510118543.8 discloses the preparation method and coating method of two kinds of coating agent of photocatalysis, this method load factor compared with
Height, but complex and immobilized catalyst is easy to fall off.Also have and various photocatalysis are made with the direct melt blending of high molecular material
Material, this method is relatively simple, but catalyst is largely coated on inside macromolecule, causes to waste.
3D printing is a kind of novel intelligent increases material manufacturing technology, is compared compared to traditional molding mode, have quickly preparation,
The advantages that fining manufacture, stock utilization height, product structure can design.Wherein fused glass pellet (FDM) is popularized the most
3D printing technique, high molecular material can be printed as the device of labyrinth by it, to meet the different demands of different application.
The present invention designs this high-specific surface area model of 24 face bodies and is conducive to improve light contact surface, and selects high light transmission resin
Then be conducive to light through matrix resin and photochemical catalyst haptoreaction.But 3D printing product translucency is not ideal enough, the present invention
By formula design and craft optimization, crystallization degree is controlled, the translucency of final product is improved.Selected photochemical catalyst 1-3
SiO is loaded for aryl oxide dendritic phthalocyanine complex2Itself also there is certain translucency, PVA cladding is carried out to it, is placed in water a side
Face can form hole, on the other hand since photochemical catalyst needs to contact with pollutant, often be wrapped up by resin with resin alloy
Firmly, it is dissolved after being handled by PVA, then avoids the problem.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of dendritic phthalocyanine@SiO2Water disposal device and
Preparation method.
In order to achieve the object of the present invention, specific technical solution is as follows:
A kind of dendritic phthalocyanine@SiO2Water disposal device is made of following weight percent compositions:
High light transmission resin 75 ~ 80
PVA coats dendritic phthalocyanine@SiO2 15~25
Dispersing agent 0.5 ~ 2
Nucleating agent 0.2 ~ 0.3；
The PVA coats dendritic phthalocyanine@SiO2As made from following methods: 5wt%PVA aqueous solution is added to 1-3 generation virtue
Ether dendritic phthalocyanine complex loads SiO2, height blendes together slurry, adds dehydrated alcohol during height is mixed, until slurry becomes powder
Material obtains PVA cladding dendritic phthalocyanine@SiO2。
The high light transmission resin is selected from polyethylene terephthalate -1,4 cyclohexane dimethanol ester (PETG), heat
Plastic polyurethane elastomer rubber (TPU), polyethylene terephthalate -1,4 cyclohexane dimethanol ester (PCTG), poly- first
One of base methyl acrylate (PMMA) is a variety of.
The dispersing agent is at least a kind of to be selected from stearic acid, polyethylene wax, oxidized polyethylene wax.
The nucleating agent is sorbierite or derivatives thereof.
A kind of dendritic phthalocyanine@SiO2The preparation method of water disposal device, which comprises the following steps:
(1) 5wt%PVA aqueous solution is added to 1-3 and loads SiO for aryl oxide dendritic phthalocyanine complex2, height blendes together slurry, in height
Dehydrated alcohol is added during mixed, until slurry becomes powder, obtains PVA cladding dendritic phthalocyanine SiO2；
(2) PVA obtained in high light transmission resin and step (1) is coated into dendritic phthalocyanine@SiO2It is dried in vacuo, then presses respectively
Proportion is placed in high mixer and mixes with nucleating agent, dispersing agent, obtains mixture；
(3) mixture obtained in step (2) is made into material by double screw extruder melting extrusion, obtains blended particles, then will
Blended particles are added to progress extrusioning shaping winding in the single screw extrusion machine of 3D wire rod production line, obtain 3D printing wire rod；
(4) 24 face bodies of high-ratio surface will be printed as obtained in step (3) by 3D printer, obtain dendritic phthalocyanine@SiO2
Water disposal device.
The dendritic phthalocyanine@SiO2Water disposal device is applied to catalytic degradation phenol.
After adopting the above technical scheme, the present invention have the advantages that following features and: 1, preparation method is simple and efficient, and device can
Recycling；2, the recycling of powder photocatalyst difficulty is solved the problems, such as；3, it can apply to catalytic degradation phenol.
Detailed description of the invention
Fig. 1 is using dendritic phthalocyanine@SiO prepared by the embodiment of the present invention 12Water disposal device outline drawing.
Fig. 2 is using dendritic phthalocyanine@SiO prepared by the embodiment of the present invention 12The multiple catalytic degradation benzene of water disposal device
Phenol active control figure.
Specific embodiment
Embodiment 1
A kind of dendritic phthalocyanine@SiO2Water disposal device is made of following weight percent compositions:
PETG 84
PVA coats dendritic phthalocyanine@SiO2 15
Stearic acid 0.7
Sorbierite 0.3
Above-mentioned dendritic phthalocyanine@SiO2The preparation method of water disposal device, comprising the following steps:
(1) 5wt%PVA aqueous solution is added to 1.5 kg 1-3 and loads SiO for aryl oxide dendritic phthalocyanine complex2, 1000rpm high
Slurry is blended together, adds dehydrated alcohol during height is mixed, until slurry becomes powder, obtains PVA cladding dendritic phthalocyanine
SiO2；
(2) 1.5 kg PVA obtained in 8.4 kg PETG after vacuum drying and step (1) are coated into dendritic phthalocyanine@SiO2
It is placed in high mixer and mixes with 0.07kg stearic acid, 0.03kg sorbierite, obtain mixture；
(3) mixture obtained in step (2) is made into material by double screw extruder melting extrusion, obtains blended particles, barrel
Temperature is followed successively by 170,180,185,195,200,205,215,220,215,210 DEG C, screw speed 185rpm/min；Again
Blended particles are added to progress extrusioning shaping winding, barrel temperature in the single screw extrusion machine of 3D wire rod production line to be followed successively by
175,190,210,220,215 DEG C, screw speed 24rpm/min obtains 3D printing wire rod；
(4) 24 face bodies of high-ratio surface will be printed as obtained in step (3) by 3D printer, 220 DEG C of print temperature, must be set
Dendritic phthalocyanine@SiO2Water disposal device.
It (is placed in double glazing collet (logical condensed water), optical filter guarantees incident light wave using 500 w tungsten halogen lamps as light source
Long λ is between 420-800 nm), it is 1.35 × 10 in 250mL concentration-4Dendroid phthalein is added in the phenol solution of mol/L
Cyanines@SiO2Water disposal device (3.0g) carries out photocatalytic degradation experiment, and phenol solution is taken to carry out ultraviolet-visible light per hour
Spectrum analysis (determines that phenol solution concentration changes in degradation process according to light absorption value at 233 nm of sample), amounts to 5 hours；It returns
It receives product to be repeated twice according to the above method, obtains dendritic phthalocyanine@SiO2Water disposal device is repeatedly catalyzed under visible light conditions
Degradation of phenol activity figure, it is specific as shown in Figure 2.
Embodiment 2
A kind of dendritic phthalocyanine@SiO2Water disposal device is made of following weight percent compositions:
TPU 74
PVA coats dendritic phthalocyanine@SiO2 25
Polyethylene wax 0.7
Sorbierite 0.3
Above-mentioned dendritic phthalocyanine@SiO2The preparation method of water disposal device, comprising the following steps:
(1) 5wt%PVA aqueous solution is added to 2.5 kg 1-3 and loads SiO for aryl oxide dendritic phthalocyanine complex2, 1000rpm high
Slurry is blended together, adds dehydrated alcohol during height is mixed, until slurry becomes powder, obtains PVA cladding dendritic phthalocyanine
SiO2；
(2) 1.5 kg PVA obtained in 7.4 kg TPU after vacuum drying and step (1) are coated into dendritic phthalocyanine@SiO2With
0.07kg polyethylene wax, 0.03kg sorbierite are placed in high mixer and mix, and obtain mixture；
(3) mixture obtained in step (2) is made into material by double screw extruder melting extrusion, obtains blended particles, barrel
Temperature is followed successively by 160,170,180,185,190,195,200,200,195,190 DEG C, screw speed 150rpm/min；Again
Blended particles are added to progress extrusioning shaping winding, barrel temperature in the single screw extrusion machine of 3D wire rod production line to be followed successively by
175,185,195,195,190 DEG C, screw speed 30rpm/min obtains 3D printing wire rod；
(4) 24 face bodies of high-ratio surface will be printed as obtained in step (3) by 3D printer, 200 DEG C of print temperature, must be set
Dendritic phthalocyanine@SiO2Water disposal device.
Embodiment 3
A kind of dendritic phthalocyanine@SiO2Water disposal device is made of following weight percent compositions:
PCTG 78
PVA coats dendritic phthalocyanine@SiO2 20
Oxidized polyethylene wax 1.8
Sorbierite 0.2
Above-mentioned dendritic phthalocyanine@SiO2The preparation method of water disposal device, comprising the following steps:
(1) 5wt%PVA aqueous solution is added to 2.0 kg 1-3 and loads SiO for aryl oxide dendritic phthalocyanine complex2, 1000rpm high
Slurry is blended together, adds dehydrated alcohol during height is mixed, until slurry becomes powder, obtains PVA cladding dendritic phthalocyanine
SiO2；
(2) 2.0 kg PVA obtained in 7.8 kg PCTG after vacuum drying and step (1) are coated into dendritic phthalocyanine@SiO2
It is placed in high mixer and mixes with 0.18kg oxidized polyethylene wax, 0.02kg sorbierite, obtain mixture；
(3) mixture obtained in step (2) is made into material by double screw extruder melting extrusion, obtains blended particles, barrel
Temperature is followed successively by 170,180,185,195,200,205,215,220,215,210 DEG C, screw speed 185rpm/min；Again
Blended particles are added to progress extrusioning shaping winding, barrel temperature in the single screw extrusion machine of 3D wire rod production line to be followed successively by
175,190,210,220,215 DEG C, screw speed 24rpm/min obtains 3D printing wire rod；
(4) 24 face bodies of high-ratio surface will be printed as obtained in step (3) by 3D printer, 220 DEG C of print temperature, must be set
Dendritic phthalocyanine@SiO2Water disposal device.
Embodiment 4
A kind of dendritic phthalocyanine@SiO2Water disposal device is made of following weight percent compositions:
PETG/TPU(80/20) 73
PVA coats dendritic phthalocyanine@SiO2 25
Stearic acid 1.7
Sorbierite 0.3
Above-mentioned dendritic phthalocyanine@SiO2The preparation method of water disposal device, comprising the following steps:
(1) 5wt%PVA aqueous solution is added to 2.5 kg 1-3 and loads SiO for aryl oxide dendritic phthalocyanine complex2, 1000rpm high
Slurry is blended together, adds dehydrated alcohol during height is mixed, until slurry becomes powder, obtains PVA cladding dendritic phthalocyanine
SiO2；
(2) 3.0 kg PVA obtained in 1.46kgTPU, 5.84kgPETG after vacuum drying and step (1) are coated into dendroid
Phthalocyanine@SiO2It is placed in high mixer and mixes with 0.17kg stearic acid, 0.03kg sorbierite, obtain mixture；
(3) mixture obtained in step (2) is made into material by double screw extruder melting extrusion, obtains blended particles, barrel
Temperature is followed successively by 170,180,185,195,200,205,210,215,210,205 DEG C, screw speed 200rpm/min；Again
Blended particles are added to progress extrusioning shaping winding, barrel temperature in the single screw extrusion machine of 3D wire rod production line to be followed successively by
175,190,210,215,210 DEG C, screw speed 25rpm/min obtains 3D printing wire rod；
(4) 24 face bodies of high-ratio surface will be printed as obtained in step (3) by 3D printer, 210 DEG C of print temperature, must be set
Dendritic phthalocyanine@SiO2Water disposal device.
Note: 1-3 used in above-described embodiment 1-4 loads SiO for aryl oxide dendritic phthalocyanine complex2Before inventor
" 1-3 loads SiO for aryl oxide dendritic phthalocyanine complex to the patent of invention of phase authorization2The preparation method of visible-light photocatalyst and
The product that its application " (ZL2014108005249) prepares, specific product is using Patent No. 2014108005249
The product that any preparation method in the disclosed i.e. following specific example 1-3 of specification is prepared into, the specific steps are as follows:
The 1-3 loads SiO for aryl oxide dendritic phthalocyanine complex2The preparation method of visible-light photocatalyst, including it is as follows
Step:
(1) configure containing volume fraction be 70%~95% isopropanol water solution or volume fraction be 70%~95% ethyl alcohol it is water-soluble
50~80 mL of mother liquor of liquid；
(2) concentrated ammonia liquor is added into the solution of step (1) and adjusts pH value 7~12, water-bath item of the mixed solution at 30 DEG C~70 DEG C
It is uniformly mixed under part；
(3) it is the 1- that 0.2 milliliter~1.5 milliliters of concentration are 0.001~0.02 mol/L that volume is added into the solution of step (2)
The n,N-Dimethylformamide stock solution of 3 generation aryl oxide dendritic phthalocyanine complexes is uniformly mixed it after stirring；
(4) ethyl orthosilicate is added into the solution of step (3), continuing 4~12 h of stirring is fully hydrolyzed it, finally by solution
Filtering, washing, catalyst required for 60 DEG C~110 DEG C drying to obtain.
Above-mentioned 1-3 is zinc, copper, cobalt or iron for the central atom in aryl oxide dendritic phthalocyanine complex.
Specific example 1
(1) 8 milliliters of distilled water are added in 50 milliliters of isopropanol, are stirred evenly under 65 DEG C of water bath conditions；
(2) 1 milliliter of concentrated ammonia liquor and 1 milliliter of 1-3 are added into mixed solution, and for aryl oxide dendritic phthalocyanine complex, (center is former
Son is zinc) stock solution (0.02 mol/L), continues to stir 5 min；
(3) ethyl orthosilicate of 8 mL is added into solution, continuing 12 h of stirring is fully hydrolyzed it, finally solution is filtered,
Washing (isopropanol wash 3 times 10 milliliters every time, 10 milliliters every time of distillation water washing 5 times), solid is dried under the conditions of 70 DEG C
It is dry, required 1-3, which is obtained, for aryl oxide dendritic phthalocyanine complex (central atom is zinc) loads SiO2Catalyst.
Specific example 2
(1) 10 milliliters of distilled water are added in 50 milliliters of dehydrated alcohol, are stirred evenly under 65 DEG C of water bath conditions；
(2) 1 milliliter of concentrated ammonia liquor and 0.5 milliliter of 1-3 are added into mixed solution for aryl oxide dendritic phthalocyanine complex (center
Atom is zinc) stock solution (0.01 mol/L), continues to stir 5 min；
(3) ethyl orthosilicate of 8 mL is added into solution, continuing 8 h of stirring is fully hydrolyzed it, finally filters solution, washes
Wash (isopropanol wash 3 times 10 milliliters every time, 10 milliliters every time of distillation water washing 5 times), solid is dried under the conditions of 70 DEG C
It is dry, required 1-3, which is obtained, for aryl oxide dendritic phthalocyanine complex (central atom is zinc) loads SiO2Catalyst.
Specific example 3
(1) 8 milliliters of distilled water are added in 50 milliliters of isopropanol, are stirred evenly under 65 DEG C of water bath conditions；
(2) be added into mixed solution 0.46 milliliter of concentrated ammonia liquor and 1 milliliter of 1-3 for aryl oxide dendritic phthalocyanine complex (in
Heart atom is zinc) stock solution (0.02 mol/L), continues to stir 5 min；
(3) ethyl orthosilicate of 8 mL is added into solution, continuing 12 h of stirring is fully hydrolyzed it, finally solution is filtered,
Washing (isopropanol wash 3 times 10 milliliters every time, 10 milliliters every time of distillation water washing 5 times), solid is dried under the conditions of 70 DEG C
It is dry, obtain required catalyst.
Above-mentioned specific embodiment is the further description to the present patent application, but the claims in the present invention are protected
Range be not limited to range described in embodiment, it is all using equivalent replacement or the technical solution of equivalent deformation,
Fall in the protection scope of the claims in the present invention.
Claims (6)
1. a kind of dendritic phthalocyanine@SiO2Water disposal device, which is characterized in that be made of following weight percent compositions:
High light transmission resin 73 ~ 84；
PVA coats dendritic phthalocyanine@SiO2 15~25；
Dispersing agent 0.5 ~ 2；
Nucleating agent 0.2 ~ 0.3；
The PVA coats dendritic phthalocyanine@SiO2As made from following methods: 5wt%PVA aqueous solution is added to 1-3 for aryl oxide
Dendritic phthalocyanine complex loads SiO2, height blendes together slurry, adds dehydrated alcohol during height is mixed, until slurry becomes powder
Material obtains PVA cladding dendritic phthalocyanine@SiO2。
2. a kind of dendritic phthalocyanine@SiO according to claim 12Water disposal device, which is characterized in that the high light transmission
Resin is selected from polyethylene terephthalate -1,4 cyclohexane dimethanol ester (PETG), thermoplastic polyurethane elastomer rubber
(TPU), polyethylene terephthalate -1,4 cyclohexane dimethanol ester (PCTG), in polymethyl methacrylate (PMMA)
It is one or more.
3. a kind of dendritic phthalocyanine@SiO according to claim 12Water disposal device, which is characterized in that the dispersing agent
It is at least a kind of to be selected from stearic acid, polyethylene wax, oxidized polyethylene wax.
4. a kind of dendritic phthalocyanine@SiO according to claim 12Water disposal device, which is characterized in that the nucleating agent
For sorbierite or derivatives thereof.
5. a kind of dendritic phthalocyanine@SiO described in claim 1-4 any one2The preparation method of water disposal device, feature
It is, comprising the following steps:
(1) 5wt%PVA aqueous solution is added to 1-3 and loads SiO for aryl oxide dendritic phthalocyanine complex2, height blendes together slurry, mixed in height
Dehydrated alcohol is added in the process, until slurry becomes powder, obtains PVA cladding dendritic phthalocyanine@SiO2；
(2) PVA obtained in high light transmission resin and step (1) is coated into dendritic phthalocyanine@SiO2It is dried in vacuo, then presses respectively
Proportion is placed in high mixer and mixes with nucleating agent, dispersing agent, obtains mixture；
(3) mixture obtained in step (2) is made into material by double screw extruder melting extrusion, obtains blended particles, then will
Blended particles are added to progress extrusioning shaping winding in the single screw extrusion machine of 3D wire rod production line, obtain 3D printing wire rod；
(4) 24 face bodies of high-ratio surface will be printed as obtained in step (3) by 3D printer, obtain dendritic phthalocyanine@SiO2Water
Processing apparatus.
6. a kind of dendritic phthalocyanine@SiO according to claim 1 to 42Water disposal device, or according to claim 5 institute
Dendritic phthalocyanine@SiO made from the preparation method stated2Water disposal device, it is characterised in that: the dendritic phthalocyanine@SiO2At water
It manages device and is applied to catalytic degradation phenol.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107698945A (en) * | 2017-08-10 | 2018-02-16 | 福建师范大学 | A kind of PETG/ dendritic phthalocyanines load SiO with photocatalysis effect2Composite wire and preparation method thereof |
| US20180370119A1 (en) * | 2017-03-17 | 2018-12-27 | Capco, Llc | Energetic thermoplastic filaments for additive manufacturing and methods for their fabrication |
| CN109135218A (en) * | 2018-06-08 | 2019-01-04 | 珠海市三绿实业有限公司 | A kind of low temperature 3D printing material and preparation method thereof |
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2019
- 2019-02-11 CN CN201910110330.9A patent/CN109880313B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180370119A1 (en) * | 2017-03-17 | 2018-12-27 | Capco, Llc | Energetic thermoplastic filaments for additive manufacturing and methods for their fabrication |
| CN107698945A (en) * | 2017-08-10 | 2018-02-16 | 福建师范大学 | A kind of PETG/ dendritic phthalocyanines load SiO with photocatalysis effect2Composite wire and preparation method thereof |
| CN109135218A (en) * | 2018-06-08 | 2019-01-04 | 珠海市三绿实业有限公司 | A kind of low temperature 3D printing material and preparation method thereof |
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Inventor after: Wu Yaling Inventor after: Huang Baoquan Inventor after: Yang Yujin Inventor after: Peng Yiru Inventor after: Chen Qinghua Inventor after: Qian Qingrong Inventor after: Xiao Liren Inventor before: Huang Baoquan Inventor before: Yang Yujin Inventor before: Peng Yiru Inventor before: Chen Qinghua Inventor before: Qian Qingrong Inventor before: Xiao Liren |
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