CN107326468A - A kind of porous photocatalytic fiber and preparation method thereof - Google Patents
A kind of porous photocatalytic fiber and preparation method thereof Download PDFInfo
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- CN107326468A CN107326468A CN201710546583.1A CN201710546583A CN107326468A CN 107326468 A CN107326468 A CN 107326468A CN 201710546583 A CN201710546583 A CN 201710546583A CN 107326468 A CN107326468 A CN 107326468A
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- Prior art keywords
- photocatalytic fiber
- porous photocatalytic
- alkali soluble
- soluble polyester
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Catalysts (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention provides a kind of porous photocatalytic fiber and preparation method thereof.The present invention, which is provided, includes sea component and the sea-island fibre of island component；The sea component is alkali soluble polyester；The island component includes alkali soluble polyester, non-alkali soluble polyester and photochemical catalyst；The alkali soluble polyester in the sea component and island component in the sea-island fibre is removed, porous photocatalytic fiber is obtained.Component of the invention by controlling sea-island fibre, one step can prepare the porous photocatalytic fiber including photochemical catalyst, due to pore structure so that photochemical catalyst is more exposed to fibrous external, increase the photochemical catalyst in fiber and the area of substrate contact, therefore the activity of fiber is improved, and then improves the catalytic degradation performance of porous photocatalytic fiber.Test result indicates that, the porous photocatalytic fiber that the present invention is provided can reach 92% for the clearance highest of methylene blue, and the more non-porous photocatalytic fiber of catalytic performance is significantly improved.
Description
Technical field
The present invention relates to catalysis material technical field, more particularly to a kind of porous photocatalytic fiber and preparation method thereof.
Background technology
Photochemical catalytic oxidation is a kind of method of the energy-efficient degradation of contaminant of comparison, by using sunshine, can be with complete
Entirely and effectively degradation of contaminant.Catalysis material is being converted into of luminous energy existed using nature under the irradiation of light
Energy needed for learning reaction produces catalytic action, make surrounding oxygen and hydrone be excited into great oxidizing force freely bear from
Son, itself do not change the material that can but promote chemical reaction to carry out.
Catalysis material has antibiotic property, air cleaning, deodorization, mould proof, anti-algae, the effect of anti-fouling and self-cleaning, almost separable
Solution is all to human body and environment harmful organic substance and part inorganic substances.Meanwhile, catalysis material has high safety
Property, or even can be as food and medicine additive, by food and medicine Surveillance Authority of the U.S. (FDA) certification, use is very safe.
Simultaneously as catalysis material provide only the place of reaction, itself is simultaneously not involved in chemical reaction, with good lasting
Property.
Photocatalytic fiber is one kind in catalysis material, and prior art typically uses modern complex technique by nano-silica
Change titanium and realize perfect adaptation with high polymer material, then by melt spinning, nano titanium oxide can be uniformly distributed among fiber,
Realize application of the photocatalyst technology in textile.But, the photocatalytic fiber but generally existing photocatalysis that prior art is provided
The problem of degradation effect is poor.
The content of the invention
It is an object of the invention to provide a kind of porous photocatalytic fiber and preparation method thereof.The preparation side that the present invention is provided
The Photocatalytic Degradation Property of porous photocatalytic fiber prepared by method is excellent.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of preparation method of porous photocatalytic fiber, comprise the following steps：
There is provided includes sea component and the sea-island fibre of island component；The sea component is alkali soluble polyester；The island component bag
Include alkali soluble polyester, non-alkali soluble polyester and photochemical catalyst；
The alkali soluble polyester in the sea component and island component in the sea-island fibre is removed, porous photocatalytic fiber is obtained.
It is preferred that, the mass ratio of the sea component and island component is (20~50):(50~80).
It is preferred that, the quality of photochemical catalyst and alkali soluble polyester and the quality of non-alkali soluble polyester and it in the island component
Than for (1~30):(70~99).
It is preferred that, the mass ratio of alkali soluble polyester and non-alkali soluble polyester is (2~30) in the island component:(70~
98)。
It is preferred that, the non-alkali soluble polyester include polyethylene terephthalate, PTT,
Polybutylene terephthalate (PBT), PEN, poly butylene succinate, PLA, polyester elastomer and
The mixture of one or more of materials in PGA or the copolymer of several materials.
It is preferred that, the metal phthalocyanine of the photochemical catalyst including 0~10 mass parts, the titanium dioxide of 0~100 mass parts and
The graphite phase carbon nitride of 0~100 mass parts, is 0 when the titanium dioxide is different with the quality of graphite phase carbon nitride.
Present invention also offers porous photocatalytic fiber prepared by preparation method described in above-mentioned technical proposal, the hole optical
Catalysis fibre includes non-alkali soluble polyester and photochemical catalyst.
It is preferred that, the mass ratio of the photochemical catalyst and non-alkali soluble polyester is (1~28):(72~99).
It is preferred that, a diameter of 50~8000nm of the porous photocatalytic fiber.
It is preferred that, the aperture of the porous photocatalytic fiber is 10~400nm.
The invention provides a kind of porous photocatalytic fiber and preparation method thereof, comprise the following steps：Offer includes extra large group
The sea-island fibre of Fen Yu islands component；The sea component is alkali soluble polyester；The island component includes alkali soluble polyester, non-alkali solubility
Polyester and photochemical catalyst；The alkali soluble polyester in the sea component and island component in the sea-island fibre is removed, hole optical is obtained and urges
Chemical fibre is tieed up.Component of the invention by controlling sea-island fibre a, step can prepare the porous photocatalytic including photochemical catalyst
Fiber, due to pore structure so that photochemical catalyst is more exposed to fibrous external, increases the photochemical catalyst and substrate in fiber
The area of contact, therefore the activity of fiber is improved, and then improve the catalytic degradation performance of porous photocatalytic fiber.Experiment knot
Fruit shows that the porous photocatalytic fiber that the present invention is provided can reach 92%, catalytic for the clearance highest of methylene blue
Can more non-porous photocatalytic fiber significantly improve.
Brief description of the drawings
Fig. 1 is the non-porous photocatalytic fiber pair that the porous photocatalytic fiber that the embodiment of the present invention 1 is obtained and comparative example 1 are obtained
The discomposing effect comparison diagram of rhodamine.
Embodiment
The invention provides a kind of preparation method of porous photocatalytic fiber, comprise the following steps：
There is provided includes sea component and the sea-island fibre of island component；The sea component is alkali soluble polyester；The island component bag
Include alkali soluble polyester, non-alkali soluble polyester and photochemical catalyst；
The alkali soluble polyester in the sea component and island component in the sea-island fibre is removed, porous photocatalytic fiber is obtained.
The present invention, which is provided, includes sea component and the sea-island fibre of island component；The sea component is alkali soluble polyester；The island
Component includes alkali soluble polyester, non-alkali soluble polyester and photochemical catalyst.In the present invention, the quality of the sea component and island component
Than being preferably (20~50):(50~80), more preferably (30~40):(60~70), be most preferably (34~36):(64~
66)。
In the present invention, the quality of photochemical catalyst and the quality of alkali soluble polyester and non-alkali soluble polyester in the island component
With the ratio between be preferably (1~30):(70~99), more preferably (5~25):(75~90), be most preferably (10~20):(80~
85).In the present invention, the mass ratio of alkali soluble polyester and non-alkali soluble polyester is preferably (2~30) in the island component:(70
~98), more preferably (5~25):(75~90), be most preferably (10~20):(80~85).
The present invention does not have special restriction to the species of the alkali soluble polyester, is used using well known to those skilled in the art
In the alkali soluble polyester for preparing sea-island fibre.In the present invention, the alkali soluble polyester is preferably to introduce polyethylene glycol
With the polyester molecule chain of the monomer such as 1,3- ethylene isophthalate -5- sulfonate, more preferably including it is poly- (terephthalic acid (TPA),
5-sodium sulfo isophthalate, ethylene glycol) copolyesters, poly- (terephthalic acid (TPA), 5-sodium sulfo isophthalate, ethylene glycol, 2-
Methyl isophthalic acid, ammediol) copolyesters, poly- (terephthalic acid (TPA), 5-sodium sulfo isophthalate, ethylene glycol, 1,3-PD) altogether
Polyester, poly- (terephthalic acid (TPA), 5-sodium sulfo isophthalate, butanediol) copolyesters or poly- (terephthalic acid (TPA), isophthalic diformazan
Acid -5- sodium sulfonates, hexylene glycol) copolyesters.In the present invention, the regularity of the macromolecular of the alkali soluble polyester is destroyed, and is made
It is soluble in hot diluted alkaline water.
In the present invention, the non-alkali soluble polyester is preferably poly- includes ethylene glycol terephthalate, poly terephthalic acid
Propylene glycol ester, polybutylene terephthalate (PBT), PEN, poly butylene succinate, PLA, polyester
The mixture of one or more of materials in elastomer and PGA or the copolymer of several materials, more preferably one kind, two
Kind, the mixture of three kinds, four kinds, five kinds, six kinds, seven kinds or eight kinds materials or one kind, two kinds, three kinds, four kinds, five kinds, six kinds,
The copolymer of seven kinds or eight kinds materials；More specifically, such as polyethylene terephthalate and PTT
Copolymer, the copolymer of PTT and polybutylene terephthalate (PBT) etc..
The present invention originates without special requirement to the non-alkali soluble polyester, using well known to those skilled in the art
Commercially available prod is prepared according to this area conventional technical means.
In the present invention, the photochemical catalyst preferably includes the metal phthalocyanine of 0~10 mass parts, the two of 0~100 mass parts
The graphite phase carbon nitride of titanium oxide and 0~100 mass parts, is 0 when the titanium dioxide is different with the quality of graphite phase carbon nitride.
In the present invention, the photochemical catalyst preferably comprises the metal phthalocyanine of 0~10 mass parts, more preferably 0.2~8 matter
Measure part, most preferably 0.4~6 mass parts.In the present invention, the metal phthalocyanine preferably has structure shown in formula 1：
In formula 1 of the present invention, the M is preferably zinc, iron, copper or cobalt；R is preferably-H ,-NH2、-Cl、-F、-
COOH、-NO2、-NHCOCH3、-NHSO3H and-SO3Any one in H.In formula 1 of the present invention, the substitution position of the R
Point is preferably meta substitution.
The present invention is for the originating without special restriction with the metal phthalocyanine of structure shown in formula 1, using ability
Metal phthalocyanine commercial goods known to field technique personnel or the metal prepared using method well known to those skilled in the art
Phthalocyanine product.
In the present invention, the photochemical catalyst preferably comprises the titanium dioxide of 0~100 mass parts, more preferably 20~80
Mass parts, most preferably 40~60 mass parts.In the present invention, the titanium dioxide is preferably rutile-type and/or anatase titanium dioxide；
The particle diameter of the titanium dioxide is preferably 50~800nm, more preferably 100~600nm, most preferably 200~500nm.This hair
The bright source to the titanium dioxide is without special restriction, using commercially available prod well known to those skilled in the art or according to this
It is prepared by preparation method known to art personnel.
In the present invention, the photochemical catalyst preferably comprises the graphite phase carbon nitride of 0~100 mass parts, more preferably 20
~80 mass parts, most preferably 40~60 mass parts.The present invention originates without special restriction to the graphite phase carbon nitride,
Prepared using commercially available prod well known to those skilled in the art or according to preparation method well known to those skilled in the art.
In the present invention, when containing metal phthalocyanine in the photochemical catalyst, the preparation method of the photochemical catalyst is preferred
Comprise the following steps：
(1) graphite phase carbon nitride and/or titanium dioxide and aprotic organic solvent are mixed, obtains mixed dispersion liquid；Will
Metal phthalocyanine with structure described in formula 1 is mixed with aprotic organic solvent, obtains metal phthalocyanine solution；
(2) mixed dispersion liquid in the step (1) is added drop-wise in metal phthalocyanine solution, by obtained reaction solution heat into
Row reaction, obtains the photochemical catalyst.
The present invention preferably mixes aprotic organic solvent with graphite phase carbon nitride, obtains graphite phase carbon nitride dispersion liquid.
In the present invention, the concentration of the graphite phase carbon nitride dispersion liquid is preferably 1~4mg/mL, more preferably 2~3mg/mL.This hair
It is bright preferably to mix aprotic organic solvent with titanium dioxide, obtain titanium oxide dispersion.In the present invention, the titanium dioxide
The concentration of titanium dispersion liquid is preferably 1~4mg/mL, more preferably 2~3mg/mL.
The present invention does not have for the species of the aprotic organic solvent mixed with graphite phase carbon nitride and titanium dioxide
Special restriction, using aprotic organic solvent well known to those skilled in the art.In the present invention, it is described non-proton to have
Machine solvent preferably includes dimethyl sulfoxide (DMSO), N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE.
In the present invention, the mixing of the aprotic organic solvent and graphite phase carbon nitride or titanium dioxide is preferably in ultrasound
Under the conditions of carry out.The present invention is operated without special restriction for described ultrasonic, using energy well known to those skilled in the art
Enough ultrasonic technical schemes being dispersed in graphite phase carbon nitride or titanium dioxide in aprotic organic solvent.In the present invention
In, the required ultrasonic time is preferably 5~30h when preparing the graphite phase carbon nitride dispersion liquid, and more preferably 9~23h is optimal
Elect 12~16h as；Required ultrasonic power is preferably 200~500W when preparing the graphite phase carbon nitride dispersion liquid；Prepare institute
The required ultrasonic time is preferably 5~30h when stating titanium oxide dispersion, more preferably 9~23h, most preferably 12~16h；
Required ultrasonic power is preferably 200~500W when preparing the titanium oxide dispersion.
When the photochemical catalyst includes graphite phase carbon nitride dispersion liquid or titanium oxide dispersion, the graphite-phase nitridation
Carbon dispersion liquid or titanium oxide dispersion are mixed dispersion liquid.When the photochemical catalyst is simultaneously including graphite phase carbon nitride and two
During titanium oxide, the present invention preferably mixes the graphite phase carbon nitride dispersion liquid and titanium oxide dispersion, obtains mixing scattered
Liquid.
In the present invention, in the mixed dispersion liquid graphite phase carbon nitride dispersion liquid and titanium oxide dispersion volume ratio
According to graphite phase carbon nitride and titanium dioxide meter.In the present invention, the graphite phase carbon nitride dispersion liquid and titanium dioxide disperse
The mixing of liquid is preferably carried out under agitation.The present invention is operated without special restriction for the stirring, using ability
Can be by graphite phase carbon nitride dispersion liquid and the technology of the well mixed stirring of titanium oxide dispersion known to field technique personnel
Scheme.In the present invention, the time of the stirring is preferably 2~10h, more preferably 4~8h, most preferably 5~7h.
The present invention preferably mixes the metal phthalocyanine with structure described in formula 1 with aprotic organic solvent, obtains metal phthalein
Cyanines solution.In the present invention, the mass concentration of the metal phthalocyanine solution is preferably 0.5~5%, and more preferably 1~4%, most
Preferably 2~3%.The present invention is for the aprotic organic solvent mixed with the metal phthalocyanine of structure described in formula 1
Species does not have special restriction, using aprotic organic solvent well known to those skilled in the art.In the present invention, it is described
Aprotic organic solvent preferably includes dimethyl sulfoxide (DMSO), N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N- methyl pyrroles
Pyrrolidone.
In the present invention, the mixing of the metal phthalocyanine and aprotic organic solvent is carried out preferably under ultrasound condition.This
Invention is for the ultrasonic operation without special restriction, and being known using those skilled in the art will have described in formula 1
The metal phthalocyanine of structure is dispersed in the ultrasonic technical scheme in aprotic organic solvent.In the present invention, the ultrasound
Time be preferably 5~30h, more preferably 9~23h, most preferably 12~16h；The ultrasonic power is preferably 200~
500W。
Obtain after the mixed dispersion liquid and the metal phthalocyanine solution, the mixed dispersion liquid is added drop-wise to gold by the present invention
Belong in phthalocyanine solution, the heating of obtained reaction solution is reacted, photochemical catalyst is obtained.In the present invention, the speed of the dropwise addition
Rate is preferably 50~150mL/h, more preferably 80~120mL/h, most preferably 95~105mL/h.In the present invention, it is described to add
The temperature of heat is preferably 45~60 DEG C, more preferably 50~55 DEG C；The time of the reaction is preferably 4~8h, more preferably 5~
7h。
After the completion of reaction, the present invention is preferably post-processed the material obtained after the reaction, obtains photochemical catalyst.
In the present invention, the post processing preferably includes following steps：
The material obtained after reaction is filtered successively, washed, is dried, photochemical catalyst is obtained.
The present invention is operated without special restriction for the filtering, using filtering well known to those skilled in the art
Technical scheme.The filtering is carried out present invention preferably employs G6 sand core funnels.
In the present invention, aprotic organic solvent, aqueous slkali, acid solution and water washing are preferably used in the washing successively.This
Invention does not have special restriction for the species of the aprotic organic solvent, using well known to those skilled in the art non-proton
Organic solvent.In the present invention, the aprotic organic solvent preferably includes dimethyl sulfoxide (DMSO), N, N- dimethyl formyls
Amine, DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE.In the present invention, the number of times washed with aprotic organic solvent is preferred
For 2~5 times.
The present invention does not have special restriction for the aqueous slkali, is using aqueous slkali well known to those skilled in the art
Can.In an embodiment of the present invention, it is specific that aqueous slkali is used as using sodium hydroxide solution.In the present invention, the aqueous slkali
Concentration is preferably 0.1~0.3mol/L.In the present invention, the number of times washed with aqueous slkali is preferably 2~5 times.
The present invention does not have special restriction for the acid solution, is using acid solution well known to those skilled in the art
Can.In an embodiment of the present invention, it is specific that acid solution is used as using sulfuric acid solution.In the present invention, the concentration of the acid solution
Preferably 0.1~0.3mol/L.In the present invention, it is preferably 2~5 times with the number of times of acid solution wash.
The present invention does not have special restriction for the species of the water, using water well known to those skilled in the art.
Present invention preferably employs ultra-pure water.The present invention does not have special restriction for the number of times being washed with water, can be by acid solution wash
The product obtained afterwards is washed to neutrality.
Complete after washing, the product obtained after the washing is dried the present invention, obtains photochemical catalyst.The present invention is right
There is no special restriction in the drying, using the technical scheme of drying well known to those skilled in the art.The present invention is excellent
Choosing is using freeze-drying.In the present invention, the temperature of the freeze-drying is preferably -60 DEG C~-40 DEG C, more preferably -55 DEG C
~-45 DEG C；The time of the freeze-drying is preferably 16~24h, more preferably 18~22h.
When not containing metal phthalocyanine in the photochemical catalyst, the present invention is preferably directly by graphite phase carbon nitride and titanium dioxide
Titanium proportionally requires to be mixed.
Source no particular/special requirement of the invention to the sea-island fibre, using island well-known to those skilled in the art
Prepared by the preparation method of fiber, can be specifically polymer composite spinning method or co-blended spinning method.
Obtain after sea-island fibre, the alkali solubility that the present invention is removed in sea component and island component in the sea-island fibre gathers
Ester, obtains porous photocatalytic fiber.Specific reality of the present invention to the alkali soluble polyester in the removal sea component and island component
The mode of applying does not have particular/special requirement, is carried out using method well-known to those skilled in the art.Subtract present invention preferably uses alkali
Amount processing removes the alkali soluble polyester in the sea component and island component.
In the present invention, the mass ratio of sea-island fibre and treatment fluid is preferably 1 during the alkali decrement treatment:(30~
50), more preferably 1:(35~45), most preferably 1:(38~43).In the present invention, the treatment fluid preferably comprises hydroxide
Sodium, accelerator and water.In the present invention, concentration of the sodium hydroxide in treatment fluid is preferably 5~30g/L, more preferably
10~25g/L, most preferably 15~20g/L.
In the present invention, the accelerator is preferably dodecyl benzyl dimethyl ammonium chloride, trimethyl bromine
Change ammonium, cetyl trimethylammonium bromide, octadecyldimethyl hydroxyethyl ammonium nitrate and N, N '-polyoxyethylene groups alkyl benzyl
One or more in ammonium chloride.In the present invention, concentration of the accelerator in treatment fluid is preferably 0.2~2g/L, more
Preferably 0.5~1.5g/L, most preferably 0.8~1.2g/L.
In the present invention, the temperature of the alkali decrement treatment is preferably 60~100 DEG C, more preferably 70~90 DEG C, optimal
Elect 75~85 DEG C as；The time of the alkali decrement treatment is preferably 20~120min, more preferably 40~100min, is most preferably
60~80min.
The fiber that preferred pair alkali decrement treatment of the present invention is obtained is washed.The present invention is wanted to the washing without special
Ask, can be by the fiber wash to neutrality.
After the washing, the fiber after the washing is dried the present invention, obtains porous photocatalytic fiber.At this
In invention, the temperature of the drying is preferably 60~100 DEG C, more preferably 70~90 DEG C, most preferably 75~85 DEG C.
It is described many present invention also offers the porous photocatalytic fiber that preparation method described in above-mentioned technical proposal is prepared
Aperture photocatalysis fiber includes non-alkali soluble polyester and photochemical catalyst.
In the present invention, the mass ratio of the photochemical catalyst and non-alkali soluble polyester is preferably (1~28):(72~99),
More preferably (10~25):(80~95), be most preferably (15~20):(85~90).
In the present invention, the diameter of the porous photocatalytic fiber is preferably 50~8000nm, more preferably 100~
4000nm, most preferably 250~2000nm.
In the present invention, the aperture of the porous photocatalytic fiber is preferably 10~400nm, more preferably 50~300nm,
Most preferably 100~200nm.
The preparation method that the present invention is provided is by controlling the component of sea-island fibre, and a step can be prepared including photocatalysis
The porous photocatalytic fiber of agent, due to pore structure so that photochemical catalyst is more exposed to fibrous external, is increased in fiber
Photochemical catalyst and the area of substrate contact, therefore the activity of fiber is improved, and then improve the catalysis of porous photocatalytic fiber
Degradation property.
Porous photocatalytic fiber provided with reference to embodiment the present invention and preparation method thereof is described in detail,
But they can not be interpreted as limiting the scope of the present invention.
In following embodiments of the invention, unless otherwise specified, the number is mass parts.
Embodiment 1
Weigh 20 parts of alkali solubility polyethylene terephthalates and 80 parts of island components carry out composite spinning, obtain island fine
Dimension.The island component includes 56 parts of PTTs, and 16 parts of alkali solubility polyethylene terephthalates (account for island
Component 20%), 8 parts of photochemical catalyst (100% TiO2)。
Then 100 parts of sea-island fibre is weighed with 1:50 bath raio adds in alkali decrement treatment liquid and handles 30min, the alkali
The concentration of sodium hydroxide is 30g/L in decrement treatment liquid, and the concentration of accelerator dodecyl benzyl dimethyl ammonium chloride is 1g/L,
100 DEG C of water temperature.Then neutrality is washed to, drying of tiling is placed in 120 DEG C of baking ovens, that is, obtains dissolving in sea component and island component
The porous photocatalytic fiber of alkali solubility polyethylene terephthalate.Claim its quality, it is about 33% to calculate its alkali mass loss rate.
Comparative example 1
Preparation method according to embodiment 1 is prepared in sea-island fibre, island component without alkali solubility poly terephthalic acid second
Diol ester, obtains non-porous photocatalytic fiber.
The non-porous photocatalytic fiber that the porous photocatalytic fiber and comparative example 1 that embodiment 1 is obtained are obtained is in simulated solar
To methylene blue, (concentration is 2 × 10 under light-5Mol/L photocatalytic degradation experiment, experimental result) are carried out as shown in figure 1, Fig. 1 is this
Decomposition of the non-porous photocatalytic fiber that the porous photocatalytic fiber and comparative example 1 that inventive embodiments 1 are obtained are obtained to rhodamine is imitated
Fruit comparison diagram.As shown in Figure 1, the porous photocatalytic fiber that embodiment 1 is provided is higher for the clearance of methylene blue, and highest can
Up to 92%, the non-porous photocatalytic fiber of comparative example 1 is only 80% for the clearance of methylene blue.
Embodiment 2
Weigh 30 parts of alkali solubility polyethylene terephthalates and 70 parts of island components carry out composite spinning, obtain island and surpass
Thin porous photocatalytic fiber.The island component includes 53 parts of polyethylene terephthalates, 7 parts of alkali solubility poly terephthalic acids
Glycol ester (account for island component 10%), 10 parts of composite catalyst (80% TiO2With 20% g-C3N4)。
The preparation method of wherein composite photo-catalyst is, by graphite phase carbon nitride and titanium dioxide in N, N- dimethyl formyls
Mixed in amine, obtain mixed dispersion liquid, be placed in ultrasound 10h in ultrasonic device.Later respectively with N,N-dimethylformamide, washing 3
All over the composite catalyst for obtaining graphite phase carbon nitride and titanium dioxide, freeze-drying is placed in, fine catalyst is obtained.
Then 100 parts of sea-island fibre is weighed with 1:30 bath raio adds in alkali decrement treatment liquid and handles 60min, the alkali
The concentration of sodium hydroxide is 10g/L in decrement treatment liquid, and the concentration of accelerator cetyl trimethylammonium bromide is 0.4g/L, water
90 DEG C of temperature.Then neutrality is washed to, drying of tiling is placed in 60 DEG C of baking ovens, that is, obtains dissolving alkali soluble in sea component and island component
The porous photocatalytic fiber of property polyethylene terephthalate.Claim its quality, it is about 32% to calculate its alkali mass loss rate.
The porous photocatalytic fiber that the present invention is obtained in the way of embodiment 1 to the present embodiment is detected, is detected
As a result show, the porous photocatalytic fiber that the present embodiment is provided is 94% for the clearance of methylene blue.
Embodiment 3
Weigh 20 parts of alkali solubility polyethylene terephthalates and 80 parts of island components carry out composite spinning, obtain island and surpass
Thin porous photocatalytic fiber.The island component includes 60 parts of polybutylene terephthalate (PBT)s, 8 parts of alkali solubility poly terephthalic acids
Glycol ester (account for island component 10%), 12 parts of composite catalyst (70% TiO2, 27% g-C3N4With 3% iron-phthalocyanine).
The preparation method of wherein composite photo-catalyst is, by graphite phase carbon nitride and titanium dioxide in N, N- dimethyl formyls
Mixed in amine, obtain mixed dispersion liquid, be placed in ultrasound 10h in ultrasonic device.Iron-phthalocyanine is dissolved into DMF,
Obtain metal phthalocyanine solution.The graphite phase carbon nitride and the mixed dispersion liquid of titanium dioxide that ultrasound is obtained again are added drop-wise to metal phthalein
In cyanines solution, obtained reaction solution heating condensing reflux is reacted, the composite photo-catalyst is obtained, respectively with N, N- bis-
NMF, washing obtain the composite catalyst of graphite phase carbon nitride and titanium dioxide for 3 times, are placed in freeze-drying, obtain powder
Last catalyst.
Then 100 parts of sea-island fibre is weighed with 1:40 bath raio adds in alkali decrement treatment liquid and handles 60min, the alkali
The concentration of sodium hydroxide is 5g/L in decrement treatment liquid, and the concentration of accelerator octadecyldimethyl hydroxyethyl ammonium nitrate is 2g/
L, 60 DEG C of water temperature.Then neutrality is washed to, drying of tiling is placed in 60 DEG C of baking ovens, that is, obtains dissolving the porous photocatalytic of sea component
Fiber.Claim its quality, it is about 25% to calculate its alkali mass loss rate.
The porous photocatalytic fiber that the present invention is obtained in the way of embodiment 1 to the present embodiment is detected, is detected
As a result show, the porous photocatalytic fiber that the present embodiment is provided is 93% for the clearance of methylene blue.
Embodiment 4
Weigh 40 parts of alkali solubility polyethylene terephthalates and 60 parts of island components carry out composite spinning, obtain island and surpass
Thin porous photocatalytic fiber.The island component includes 44 parts of poly butylene succinates, 12 parts of alkali solubility poly terephthalic acid second
Diol ester (account for island component 10%), 4 parts of composite catalyst (80% TiO2, 19% g-C3N4With 1% tetramino zinc phthalein
Cyanines).Wherein the preparation method of composite photo-catalyst is referring to embodiment 3.
Then 100 parts of sea-island fibre is weighed with 1:30 bath raio adds in alkali decrement treatment liquid and handles 60min, the alkali
The concentration of sodium hydroxide is 20g/L in decrement treatment liquid, accelerant N, and the concentration of N '-polyoxyethylene groups alkyl benzyl ammonium chloride is
0.5g/L, 80 DEG C of water temperature.Then neutrality is washed to, drying of tiling is placed in 80 DEG C of baking ovens, that is, obtains dissolving the porous of sea component
Photocatalytic fiber.Claim its quality, it is about 42% to calculate its alkali mass loss rate.
The porous photocatalytic fiber that the present invention is obtained in the way of embodiment 1 to the present embodiment is detected, is detected
As a result show, the porous photocatalytic fiber that the present embodiment is provided is 97% for the clearance of methylene blue.
As seen from the above embodiment, the preparation method that the present invention is provided is simple and easy to control, by controlling the component of sea-island fibre,
One step can prepare the porous photocatalytic fiber including photochemical catalyst, due to pore structure so that photochemical catalyst more exposes
In fibrous external, the photochemical catalyst in fiber and the area of substrate contact, the catalysis of obtained porous photocatalytic fiber are increased
The more non-porous photocatalytic fiber of degradation property is significantly improved.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of porous photocatalytic fiber, comprises the following steps：
There is provided includes sea component and the sea-island fibre of island component；The sea component is alkali soluble polyester；The island component includes alkali
Dissolubility polyester, non-alkali soluble polyester and photochemical catalyst；
The alkali soluble polyester in the sea component and island component in the sea-island fibre is removed, porous photocatalytic fiber is obtained.
2. preparation method according to claim 1, it is characterised in that the sea component and the mass ratio of island component are (20
~50):(50~80).
3. preparation method according to claim 1 or 2, it is characterised in that in the island component quality of photochemical catalyst with
The quality of alkali soluble polyester and non-alkali soluble polyester and the ratio between be (1~30):(70~99).
4. preparation method according to claim 3, it is characterised in that alkali soluble polyester and non-alkali solubility in the island component
The mass ratio of polyester is (2~30):(70~98).
5. preparation method according to claim 1, it is characterised in that the non-alkali soluble polyester includes poly terephthalic acid
Glycol ester, PTT, polybutylene terephthalate (PBT), PEN, polybutadiene
The mixtures of one or more of materials in sour butanediol ester, PLA, polyester elastomer and PGA or several materials
Copolymer.
6. preparation method according to claim 1, it is characterised in that the photochemical catalyst includes the gold of 0~10 mass parts
Belong to the graphite phase carbon nitride of phthalocyanine, the titanium dioxide of 0~100 mass parts and 0~100 mass parts, the titanium dioxide and graphite
It is 0 when the quality of phase carbon nitride is different.
7. the porous photocatalytic fiber that preparation method described in claim 1~6 any one is prepared, the porous photocatalytic
Fiber includes non-alkali soluble polyester and photochemical catalyst.
8. porous photocatalytic fiber according to claim 7, it is characterised in that the photochemical catalyst and non-alkali soluble polyester
Mass ratio be (1~28):(72~99).
9. the porous photocatalytic fiber according to claim 7 or 8, it is characterised in that the porous photocatalytic fiber it is straight
Footpath is 50~8000nm.
10. porous photocatalytic fiber according to claim 9, it is characterised in that the aperture of the porous photocatalytic fiber
For 10~400nm.
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