CN108728933A - A kind of compound colored light catalysis fibre of core-skin type and its preparation method and application - Google Patents
A kind of compound colored light catalysis fibre of core-skin type and its preparation method and application Download PDFInfo
- Publication number
- CN108728933A CN108728933A CN201810584259.3A CN201810584259A CN108728933A CN 108728933 A CN108728933 A CN 108728933A CN 201810584259 A CN201810584259 A CN 201810584259A CN 108728933 A CN108728933 A CN 108728933A
- Authority
- CN
- China
- Prior art keywords
- core
- compound
- present
- titanium dioxide
- colored light
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
-
- 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
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic System
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
Abstract
The present invention provides a kind of compound colored light catalysis fibres of core-skin type, belong to field of photocatalytic material.Including cortex and sandwich layer, the sandwich layer includes polyester and sandwich layer Masterbatch；The cortex includes polymer substrate, cortex Masterbatch and photochemical catalyst, and the polymer substrate includes polyester and/or polyamide, and the photochemical catalyst partial denudation is in cortical surface, and the photochemical catalyst dispersion is in the polymer matrix.Photochemical catalyst is suitably exposed in cortical surface for photochemical catalyst partial denudation in the present invention, improves the photocatalysis performance of the compound colored light catalysis fibre of core-skin type as much as possible.Embodiment statistics indicate that, the compound colored light catalysis fibre of core-skin type provided by the invention is very high for the degradation rate of methylene blue, and can degrade all methylene blues (a concentration of 2 × 10 at 40 minutes or so‑5mol/L)。
Description
Technical field
The present invention relates to catalysis material technical field more particularly to a kind of compound colored light catalysis fibre of core-skin type and its
Preparation method and application.
Background technology
Bonding force of the core-sheath compound fibre between its cortex component and sandwich layer component requires to be not so good as property fiber knot arranged side by side
Structure is stringent, therefore larger to the selectivity of fibre fractionation when changing fibre property, while core-skin composite fiber can not only be drawn
Take the advantage of cortex, core material respectively, additionally it is possible to obtain the specific function that core-skin type morphosis is assigned.Traditional core-skin
Type composite fibre is mostly used for improving hygroscopicity, antistatic property, the spinnability etc. of fiber, rare by core-sheath compound fibre and light
The research that catalysis material is combined.
Photocatalytic fiber is one kind in catalysis material, general to use modern complex technique by nano-titanium dioxide and fibre
Dimension, which combines, prepares depollution of environment textile.Modern commercial run is mainly prepared using two kinds of means of finishing method and spin processes
Depollution of environment textile.Finishing method needs to carry out leaching gadolinium either coating treatment to molding fabric, it is made to have light
Catalytic performance；And spinning rule is directly to mix photochemical catalyst with spinning solution, being then prepared by spinning technique has
The textile of catalysis.The compound colored light catalysis fibre overwhelming majority catalyst of core-skin type that conventional method obtains can be wrapped by
In fibrous inside, so that catalytic efficiency substantially reduces.
Invention content
In consideration of it, the purpose of the present invention is to provide compound colored light catalysis fibre of a kind of core-skin type and preparation method thereof and
Using.Photochemical catalyst partial denudation is in cortical surface, photocatalysis in the compound colored light catalysis fibre of core-skin type provided by the invention
Degradation property is excellent.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
A kind of compound colored light catalysis fibre of core-skin type, including cortex and sandwich layer, the sandwich layer include polyester and sandwich layer color
Master batch；The cortex includes polymer substrate, cortex Masterbatch and photochemical catalyst, the polymer substrate include polyester and/or
Polyamide, the photochemical catalyst partial denudation is in cortical surface, and the photochemical catalyst dispersion is in the polymer matrix.
Preferably, the mass content that the photochemical catalyst accounts for the compound colored light catalysis fibre of core-skin type is 3%~14%；
The total amount of the sandwich layer Masterbatch and cortex Masterbatch accounts for the mass content of the compound colored light catalysis fibre of core-skin type
It is 1%~6%.
Preferably, the photochemical catalyst include titanium dioxide, titanium dioxide-graphene complex, class graphite phase carbon nitride,
Class graphite phase carbon nitride-graphene complex, titanium dioxide-class graphite phase carbon nitride compound, titanium dioxide-tungstic acid are multiple
Close object, class graphite phase carbon nitride-tungstic acid compound, titanium dioxide-class graphite phase carbon nitride-tungstic acid compound, two
Titanium oxide-class graphite phase carbon nitride-metal phthalocyanine compound, class graphite phase carbon nitride-metal phthalocyanine compound, titanium dioxide-
Metal phthalocyanine compound, metal phthalocyanine-tungstic acid compound, class graphite phase carbon nitride-tungstic acid-metal phthalocyanine compound
With it is one or more in titanium dioxide-metal phthalocyanine-tungstic acid compound.
Preferably, the mass ratio of the sandwich layer center core layer Masterbatch and polyester is (1~10):(90~99).
Preferably, the mass ratio of cortex Masterbatch and polymer substrate is (0~10) in the cortex:(90~100).
Preferably, a diameter of 0.05~4000 μm of the compound colored light catalysis fibre of the core-skin type.
The present invention also provides the preparation methods of the compound colored light catalysis fibre of core-skin type described in above-mentioned technical proposal, including
Following steps：
(1) it shapes, cool down, oil, after drafting forming through ejection successively after melting cortex raw material and core layer raw material respectively,
Obtained Cortical fiber is wound around core fibers, obtains precursor；
(2) the partial polymer matrix in the precursor removal cortex obtained the step (1), exposes photochemical catalyst,
Obtain the compound colored light catalysis fibre of core-skin type.
Preferably, the weight content of cortex raw material is 20~80% in the precursor.
Preferably, a diameter of 0.1~5000 μm of the precursor.
The present invention also provides the compound colored light catalysis fibre of core-skin type described in above-mentioned technical proposal or above-mentioned technical proposals
Application of the compound colored light catalysis fibre of core-skin type that the preparation method obtains in photocatalytic degradation.
The present invention provides a kind of compound colored light catalysis fibres of core-skin type, including cortex and sandwich layer, the sandwich layer to include
Polyester and sandwich layer Masterbatch；The cortex includes polymer substrate, cortex Masterbatch and photochemical catalyst, the polymer substrate packet
Polyester and/or polyamide are included, the photochemical catalyst partial denudation is dispersed in polymer substrate in cortical surface, the photochemical catalyst
In.Photochemical catalyst is exposed in cortical surface for photochemical catalyst partial denudation in the present invention, improves core-skin type as much as possible
The photocatalysis performance of compound colored light catalysis fibre.Embodiment statistics indicate that, the compound colored light of core-skin type provided by the invention
Catalysis fibre is very high for the degradation rate of methylene blue, the methylene blue (concentration that can have degraded all at 40 minutes or so
It is 2 × 10-5mol/L)。
Meanwhile coloured photocatalytic fiber is obtained using Masterbatch blend spinning, it can not only reduce the damage to fibre property
Wound, and colored fibre can be made more resistant to solarization.
Further, the preparation method of the compound colored light catalysis fibre of core-skin type provided by the invention is simple for process, color masterbatch
Grain can also shorten the production cycle, solve environmental pollution caused by textile dyeing.
Description of the drawings
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is that the compound colored light catalysis fibre of core-skin type is bent to the photocatalytic degradation of methylene blue in the embodiment of the present invention 1
Line.
Specific implementation mode
The present invention provides a kind of compound colored light catalysis fibres of core-skin type, including cortex and sandwich layer, the sandwich layer to include
Polyester and sandwich layer Masterbatch；The cortex includes polymer substrate, cortex Masterbatch and photochemical catalyst, the polymer substrate packet
Polyester and/or polyamide are included, the photochemical catalyst partial denudation is dispersed in polymer substrate in cortical surface, the photochemical catalyst
In.
In the present invention, the mass content that the photochemical catalyst accounts for the compound colored light catalysis fibre of core-skin type is preferably 3~
14%, more preferably 4~13%, most preferably 5~10%.
In the present invention, the polyester in the sandwich layer preferably includes poly- pair of common polyethylene terephthalate, regeneration
Ethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate (PBT), polyethylene naphthalate
It is more preferably common poly- to benzene two with one or more of the polyglycolide mixture of substance or the copolymer of several substances
Formic acid glycol ester, regeneration polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate
The mixture of two kinds, three kinds, four kinds, five kinds or six kinds substances in ester, polyethylene naphthalate and polyglycolide, or
The copolymer of two kinds, three kinds, four kinds, five kinds or six kinds substances, most preferably common polyethylene terephthalate and poly- pair
The polymer or polyethylene naphthalate of benzene dicarboxylic acid trimethylene glycol ester and the polymer of polyglycolide.When the sandwich layer is
When mixture, the present invention does not limit the dosage of each component in the mixture, using the mixture of arbitrary proportion.
The present invention does not have the source of the copolymer special restriction, using copolymer well known to those skilled in the art
Preparation method be made.
In the present invention, the fusing point of the polyester in the sandwich layer is preferably 250~270 DEG C, more preferably 255~265 DEG C,
Most preferably 258~263 DEG C.
In the present invention, the mass ratio of the sandwich layer center core layer Masterbatch and polyester is preferably (1~10):(90~99),
More preferably (2~9):(91~98), most preferably (3~8):(92~97).
In the present invention, the photochemical catalyst preferably includes titanium dioxide, titanium dioxide-graphene complex, class graphite
Phase carbon nitride, class graphite phase carbon nitride-graphene complex, titanium dioxide-class graphite phase carbon nitride compound, titanium dioxide-
Tungstic acid compound, class graphite phase carbon nitride-tungstic acid compound, titanium dioxide-class graphite phase carbon nitride-tungstic acid
Compound, titanium dioxide-class graphite phase carbon nitride-metal phthalocyanine compound, class graphite phase carbon nitride-metal phthalocyanine compound,
Titanium dioxide-metal phthalocyanine compound, metal phthalocyanine-tungstic acid compound, class graphite phase carbon nitride-tungstic acid-metal
It is one or more in phthalocyanine compound and titanium dioxide-metal phthalocyanine-tungstic acid compound.
In the present invention, when the photochemical catalyst includes titanium dioxide；The titanium dioxide be preferably rutile-type and/or
Anatase titanium dioxide；The grain size of the titanium dioxide is preferably 50~800nm, more preferably 100~600nm, most preferably 200~
500nm；The present invention does not have particular/special requirement to the source of the titanium dioxide, uses the dioxy in source known to those skilled in the art
Change titanium, such as commercially available titanium dioxide.
In the present invention, when the photochemical catalyst includes titanium dioxide-graphene complex, the titanium dioxide-graphite
The mass ratio of titanium dioxide and graphene is preferably 100 in alkene compound:(0.1~2), more preferably 100:(0.2~1)；This
Invention does not have particular/special requirement to the source of the titanium dioxide-graphene complex, using commercially commodity or make
It is prepared with method well known to those skilled in the art.In a specific embodiment of the present invention, the titanium dioxide-stone
Black alkene compound is preferably formed by directly mixing by titanium dioxide and graphene；The present invention is not special to the type of the graphene
It is required that preferably single-layer graphene and/or multi-layer graphene；The thickness of the multi-layer graphene is preferably 0.3~50nm, more excellent
It is selected as 2~40nm.
In the present invention, when the photochemical catalyst includes class graphite phase carbon nitride, the class graphite phase carbon nitride (g-C3N4)
Type there is no particular/special requirement, preferably single layer class graphite phase carbon nitride and/or multilayer class graphite phase carbon nitride；The class graphite
The thickness of phase carbon nitride is preferably 0.3~50nm, more preferably 2~40nm；The present invention carrys out the class graphite phase carbon nitride
Source is not particularly limited, and is carried out using commercially available class graphite phase carbon nitride commodity or using method well known to those skilled in the art
It prepares.
In a specific embodiment of the present invention, the class graphite phase carbon nitride (g-C3N4) preparation method preferably include with
Lower step：Urea is heat-treated, class graphite phase carbon nitride is obtained.In the present invention, the temperature of the heat treatment is preferably
300~650 DEG C, more preferably 350~600 DEG C, most preferably 500~550 DEG C；The time of the heat treatment is preferably 3~8h,
More preferably 4~7h, most preferably 5~6h.The present invention preferably is selected from room temperature to heat treatment temperature, described to be warming up to heat treatment
The heating rate of temperature is preferably 1~6 DEG C/min, more preferably 2~4 DEG C/min.The present invention is preferably under air atmosphere, normal pressure
It is heat-treated；The present invention does not have equipment used by heat treatment special restriction, use well known to those skilled in the art
Equipment for being heat-treated, it is specific such as tube furnace or batch-type furnace.
In the present invention, when the photocatalytic fiber includes class graphite phase carbon nitride-graphene, the class graphite-phase nitridation
The mass ratio of carbon-graphite alkene is preferably 100:(0.1~2), more preferably 100:(0.2~1)；The present invention is to the class graphite-phase
The source of carbonitride-graphene complex does not have particular/special requirement, using commercially commodity or use art technology
Prepared by method known to personnel, specifically, being such as formed by directly mixing by graphite phase carbon nitride and graphene.
In the present invention, when the photochemical catalyst includes titanium dioxide-class graphite phase carbon nitride compound, the titanium dioxide
The mass ratio of titanium-class graphite phase carbon nitride compound is preferably 100:(2~100), more preferably 100：(5~25)；The present invention
There is no particular/special requirement to the source of titanium dioxide-class graphite phase carbon nitride compound, uses commercially available titanium dioxide-class graphite-phase
Nitridation carbon complex commodity are prepared using method well known to those skilled in the art, specifically, such as by titanium dioxide
Titanium and class graphite phase carbon nitride are formed by directly mixing.
In the present invention, when the photochemical catalyst includes titanium dioxide-tungstic acid compound, the titanium dioxide-three
The mass ratio of titanium dioxide and tungstic acid is preferably 100 in tungsten oxide compound:(2~1000), more preferably 100:(5~
300)；The present invention does not have particular/special requirement to the source of titanium dioxide-tungstic acid compound, uses commercially available titanium dioxide-three
Tungsten oxide compound commodity are prepared using method well known to those skilled in the art, specifically, such as by titanium dioxide
Titanium, tungstic acid are formed by directly mixing；The type of the titanium dioxide and source are consistent with said program, and details are not described herein；
The grain size of the tungstic acid is preferably 5~500nm, more preferably 10~400nm, most preferably 50~300nm.
In the present invention, when the photochemical catalyst includes class graphite phase carbon nitride-tungstic acid compound, the class graphite
The mass ratio of class graphite phase carbon nitride and tungstic acid is preferably 100 in phase carbon nitride-tungstic acid compound:(10~
1000), more preferably 100:(20~500)；The present invention is to the source of class graphite phase carbon nitride-tungstic acid compound without spy
It is different to require, using commercially available class graphite phase carbon nitride-tungstic acid compound commodity or using well known to those skilled in the art
Prepared by method, specifically, being such as formed by directly mixing by class graphite phase carbon nitride and tungstic acid；The class graphite-phase
Carbonitride and the type of tungstic acid and source are consistent with said program, and details are not described herein.
In the present invention, when the photochemical catalyst includes titanium dioxide-class graphite phase carbon nitride-tungstic acid compound,
Titanium dioxide, class graphite phase carbon nitride and tungstic acid in the titanium dioxide-class graphite phase carbon nitride-tungstic acid compound
Mass ratio be preferably (15~90):(2~50):(5~80), more preferably (30~90):(5~40):(10~70)；This hair
The bright source to the titanium dioxide-class graphite phase carbon nitride-tungstic acid compound does not have particular/special requirement, uses commercially available two
Titanium oxide-class graphite phase carbon nitride-tungstic acid compound commodity use method system well known to those skilled in the art
It is standby, specifically, being such as formed by directly mixing by titanium dioxide, class graphite phase carbon nitride and tungstic acid；It is described to be used to prepare
Raw material titanium dioxide, class graphite phase carbon nitride, the tungstic acid of titanium dioxide-class graphite phase carbon nitride-tungstic acid compound
Type and source it is consistent with said program, details are not described herein.
In the present invention, when the photochemical catalyst includes titanium dioxide-class graphite phase carbon nitride-metal phthalocyanine compound,
Titanium dioxide, class graphite phase carbon nitride and metal phthalocyanine in the titanium dioxide-class graphite phase carbon nitride-metal phthalocyanine compound
Mass ratio be preferably (45~74):(25~50):(0.5~6), more preferably (55~65):(30~40):(1~4)；This
Invention does not have particular/special requirement, use commercially available in the source of the titanium dioxide-class graphite phase carbon nitride-metal phthalocyanine compound
Titanium dioxide-class graphite phase carbon nitride-metal phthalocyanine compound is prepared using method well known to those skilled in the art
?.
In the present invention, the raw material class for being used to prepare titanium dioxide-class graphite phase carbon nitride-metal phthalocyanine compound
The type and source of graphite phase carbon nitride and titanium dioxide are consistent with said program, and details are not described herein.
In the present invention, the raw material gold for being used to prepare titanium dioxide-class graphite phase carbon nitride-metal phthalocyanine compound
The structural formula for belonging to phthalocyanine is preferably as shown in Equation 1：
In formula 1 of the present invention, M is transition metal ions, and the present invention does not have the type of the transition metal ions
There is particular determination, using the transition metal ions well known to those skilled in the art that can form complex with phthalocyanine, tool
Body, such as preferably include zinc ion, iron ion, copper ion or cobalt ions；The R is-H ,-NH2、-Cl、-F、-COOH、-
NHCOCH3、-NHSO3H or-SO3The substitution site of H, R can be any one in 4 substitution sites on phenyl ring.
The present invention does not have special restriction for the source of the metal phthalocyanine with structure shown in formula 1, using ability
Metal phthalocyanine commercial goods known to field technique personnel or the metal being prepared using method well known to those skilled in the art
Phthalocyanine product, specifically, the preparation as carried out metal phthalocyanine using phthalic nitrile method or phthalic anhydride urea method, with specific reference to text
Offer the method system in (the research Institutes Of Technology Of Zhejiang of the organic pollutions such as Lv Wangyang catalysis fiber degradation dyestuffs, 2010)
It is standby.
In the present invention, when in the composite catalyst contain metal phthalocyanine when, metal phthalocyanine can be supported on other at
Divide surface (titanium dioxide, class graphite phase carbon nitride etc.), so that the ingredients such as titanium dioxide, class graphite phase carbon nitride is sensitized, widen light
The visible light respective range of catalyst improves the efficiency of light energy utilization.
In the present invention, the preparation method of the titanium dioxide-class graphite phase carbon nitride-metal phthalocyanine compound is preferably wrapped
Containing following steps：
(1) class graphite phase carbon nitride, titanium dioxide and aprotic organic solvent are mixed, obtains mixed dispersion liquid；It will tool
There is the metal phthalocyanine of structure described in formula 1 to be 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 titanium dioxide-class graphite phase carbon nitride-metal phthalocyanine compound.
The present invention preferably mixes aprotic organic solvent with class graphite phase carbon nitride and titanium dioxide respectively, and ultrasound obtains
To class graphite phase carbon nitride dispersion liquid and titanium oxide dispersion.In the present invention, the class graphite phase carbon nitride dispersion liquid
Concentration is preferably 1~4mg/mL, more preferably 2~3mg/mL.In the present invention, the concentration of the titanium oxide dispersion is preferred
For 1~4mg/mL, more preferably 2~3mg/mL.
The present invention the type of the aprotic organic solvent not mixed with class graphite phase carbon nitride and titanium dioxide
There is special restriction, using aprotic organic solvent well known to those skilled in the art.In the present invention, described non-proton
Organic solvent preferably includes dimethyl sulfoxide (DMSO), N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N-Methyl pyrrolidone.
The present invention for the not special restriction of the ultrasound, using it is well known to those skilled in the art can be by class graphite
Phase carbon nitride and titanium dioxide are dispersed in the technical solution of the ultrasound in aprotic organic solvent.In the present invention, it prepares
The time of required ultrasound is preferably 5~30h when the class graphite phase carbon nitride dispersion liquid, more preferably 9~23h, most preferably
12~16h；Power is preferably 200~500W；When preparing the titanium oxide dispersion time of required ultrasound be preferably 5~
30h, more preferably 9~23h, most preferably 12~16h；Power is preferably 200~500W.
After obtaining class graphite phase carbon nitride dispersion liquid and titanium oxide dispersion, the present invention is preferably by the class graphite-phase nitrogen
Change carbon dispersion liquid and titanium oxide dispersion mixing, stirring obtains mixed dispersion liquid.In the present invention, the mixed dispersion liquid
The volume ratio of middle class graphite phase carbon nitride dispersion liquid and titanium oxide dispersion is according to class graphite phase carbon nitride and titanium dioxide meter.
The present invention for the not special restriction of the stirring, using it is well known to those skilled in the art can be by class graphite phase carbon nitride
The technical solution of dispersion liquid and the uniformly mixed stirring of titanium oxide dispersion.In the present invention, the time of the stirring
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, and ultrasound obtains gold
Belong to phthalocyanine solution.In the present invention, the concentration of the metal phthalocyanine solution is preferably 0.5%~5%.The present invention for it is described with
The type of the aprotic organic solvent of metal phthalocyanine mixing with structure described in formula 1 does not have special restriction, using this field
Aprotic organic solvent known to technical staff.In the present invention, the aprotic organic solvent preferably includes dimethyl
Sulfoxide, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N-Methyl pyrrolidone.The present invention does not have the ultrasound
Special restriction, it is non-proton using that can be dispersed in the metal phthalocyanine with structure described in formula 1 known to those skilled in the art
The technical solution of ultrasound in organic solvent.In the present invention, the time of the ultrasound is preferably 5~30h, more preferably
9~23h, most preferably 12~16h；The power of the ultrasound is preferably 200~500W.
After obtaining 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, the photoreactivation catalyst is obtained.In the present invention, described
The rate of dropwise addition is preferably 50~150mL/h, more preferably 80~120mL/h, most preferably 95~105mL/h.In the present invention
In, the temperature of the heating is preferably 45~60 DEG C, more preferably 50~55 DEG C；The time of heating reaction is preferably 4~8h, more
Preferably 5~7h.
After the completion of the reaction, the present invention preferably post-processes the material obtained after reaction, obtains the photocatalysis
Agent.In the present invention, the post-processing preferably includes following steps：
By the material filtering obtained after reaction, washing, drying, the titanium dioxide-class graphite phase carbon nitride-metal is obtained
Phthalocyanine compound.
The present invention is for the not special restriction of the filtering, using the technical side of filtering well known to those skilled in the art
Case.Present invention preferably employs G6 sand core funnels to carry out the filtering.
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 the type of the aprotic organic solvent special restriction, 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 N-Methyl pyrrolidone.In the present invention, the number washed with aprotic organic solvent is preferred
It is 2~5 times.
The present invention does not have the aqueous slkali special restriction, is using aqueous slkali well known to those skilled in the art
It can.In an embodiment of the present invention, specifically using sodium hydroxide solution as aqueous slkali.In the present invention, the aqueous slkali
Concentration is preferably 0.1~0.3mol/L.In the present invention, it is preferably 2~5 times with the number that aqueous slkali washs.
The present invention does not have the acid solution special restriction, is using acid solution well known to those skilled in the art
It can.In an embodiment of the present invention, specifically using sulfuric acid solution as 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 acid solution wash.
The present invention does not have the type of the water special restriction, using water well known to those skilled in the art.
Present invention preferably employs ultra-pure waters.The present invention does not have the number being washed with water special restriction, can be by acid solution wash
The product obtained afterwards is washed to neutrality.
After completing the washing, the product obtained after the washing is dried the present invention, obtains the complex light and urges
Agent.The present invention is for the not special restriction of the drying, using the technical solution of drying well known to those skilled in the art
?.Present invention preferably employs freeze-dryings.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~for 24 hours, more preferably 18~22h.
In the present invention, when the catalyst includes class graphite phase carbon nitride-metal phthalocyanine compound, the class graphite-phase
The mass ratio of class graphite phase carbon nitride and metal phthalocyanine is preferably 100 in carbonitride-metal phthalocyanine compound:(0.05~10),
More preferably 100:(0.1~5)；The present invention does not have particular/special requirement to the source of class graphite phase carbon nitride-metal phthalocyanine compound,
It carries out preparing using commercially available class graphite phase carbon nitride-metal phthalocyanine commodity or using method well known to those skilled in the art
It can；In a specific embodiment of the present invention, the preparation method and above-mentioned two of the class graphite phase carbon nitride-metal phthalocyanine compound
The preparation method of titanium oxide-class graphite phase carbon nitride-metal phthalocyanine compound is similar, and content of titanium dioxide therein is become
Zero, then adjust the content of class graphite phase carbon nitride and metal phthalocyanine；It is described to be used to prepare class graphite phase carbon nitride-metal
The raw metal phthalocyanine of phthalocyanine compound and the type of class graphite phase carbon nitride and source are consistent with said program, herein no longer
It repeats.
In the present invention, when the photochemical catalyst includes titanium dioxide-metal phthalocyanine compound, the titanium dioxide-gold
It is preferably 100 to belong to the mass ratio of titanium dioxide and metal phthalocyanine in phthalocyanine compound:(0.05~10), more preferably 100:(0.1
~5)；The present invention does not have particular/special requirement to the source of titanium dioxide-metal phthalocyanine compound, uses commercially available titanium dioxide-gold
Belong to phthalocyanine commodity or is prepared using method well known to those skilled in the art；In a specific embodiment of the present invention,
The preparation method of the titanium dioxide-metal phthalocyanine compound and above-mentioned titanium dioxide-class graphite phase carbon nitride-metal phthalocyanine are multiple
The preparation method for closing object is similar, and class graphite phase carbon nitride content therein is become zero, and adjusts titanium dioxide and metal phthalocyanine
Content；It is described to be used to prepare titanium dioxide-raw metal phthalocyanine of metal phthalocyanine compound and the type of titanium dioxide
Consistent with source with said program, details are not described herein.
In the present invention, when the photochemical catalyst includes metal phthalocyanine-tungstic acid compound；The metal phthalocyanine-three
The mass ratio of metal phthalocyanine and tungstic acid is preferably (0.05~10) in tungsten oxide compound:100, more preferably (0.1~
5):100；The present invention does not have particular/special requirement to the source of class graphite phase carbon nitride-tungstic acid compound, uses commercially available class stone
Black phase carbon nitride-tungstic acid compound commodity are prepared using method well known to those skilled in the art；At this
In the specific embodiment of invention, the preparation method of the metal phthalocyanine-tungstic acid compound and above-mentioned titanium dioxide-class graphite
The preparation method of phase carbon nitride-metal phthalocyanine compound is similar, by the content of class graphite phase carbon nitride and titanium dioxide therein
It sets to zero, then adjusts the content of tungstic acid and metal phthalocyanine；It is described that be used to prepare metal phthalocyanine-tungstic acid multiple
It closes the raw metal phthalocyanine of object and the type of tungstic acid and source is consistent with said program, details are not described herein.
In the present invention, when the photochemical catalyst includes titanium dioxide-tungstic acid-metal phthalocyanine compound；Described two
The mass ratio of titanium dioxide, tungstic acid and metal phthalocyanine is preferably (10 in titanium oxide-tungstic acid-metal phthalocyanine compound
~90):(0.1~10):(5~90), more preferably (25~90):(0.2~5):(10~80)；The present invention is to the titanium dioxide
The source of titanium-tungstic acid-metal phthalocyanine compound does not have particular/special requirement, uses commercially available titanium dioxide-tungstic acid-metal
Phthalocyanine compound commodity are prepared using method well known to those skilled in the art；In specific embodiments of the present invention
In, preparation method and the above-mentioned titanium dioxide-class graphite-phase of the titanium dioxide-tungstic acid-metal phthalocyanine compound nitrogenize
The preparation method of carbon-metal phthalocyanine compound is similar, and class graphite phase carbon nitride therein is replaced with tungstic acid；It is described
It is used to prepare the raw material titanium dioxide of titanium dioxide-tungstic acid-metal phthalocyanine compound, the kind of tungstic acid and metal phthalocyanine
Class and source are consistent with said program, and details are not described herein.
In the present invention, the photochemical catalyst is two or more mixture in above-mentioned several photochemical catalysts；When
The photochemical catalyst be mixture when, the present invention in the photocatalyst mixture photochemical catalyst type and mass ratio do not have
Particular/special requirement is mixed using the photochemical catalyst of any kind with arbitrary mass ratio.
In the present invention, the fusing point of polyester is preferably 90~180 DEG C, more preferably 100~160 in the polymer substrate
DEG C, most preferably 120~140 DEG C.
In the present invention, polyester preferably includes low melting point polyethylene terephthalate, low in the polymer substrate
One or more of fusing point poly butylene succinate, the low melting point polylactic acid and polyester elastomer mixture of substance or several
The copolymer of kind substance, more preferably low melting point polyethylene terephthalate, low melting point poly butylene succinate, eutectic
Point polylactic acid and one kind, two or three of mixture or two or three of polymer in polyester elastomer, most preferably
For, the polymer or low melting point polylactic acid and low-melting point polyester of low melting point poly butylene succinate and low melting point polylactic acid
The polymer of elastomer, then low melting point poly butylene succinate, low melting point polylactic acid and low-melting point polyester elastomer three
The polymer of person.
In the present invention, polyester is preferably normal polyester in the polymer substrate, and the fusing point of the normal polyester is preferred
It is 250~270 DEG C, more preferably 255~265 DEG C, most preferably 258~263 DEG C.
In the present invention, the normal polyester preferably includes common polyethylene terephthalate, regeneration gathers to benzene two
Formic acid glycol ester, polypropylene terephthalate, polybutylene terephthalate (PBT), polyethylene naphthalate and poly-
The copolymer of the mixture of one or more of glycolide substance or several substances；More preferably common poly terephthalic acid
Glycol ester, regeneration polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate (PBT),
The mixture of one, two, three, four, five or six of substance in polyethylene naphthalate and polyglycolide, or
The polymer of two kinds, three kinds, four kinds, five kinds or six kinds substances of person more preferably regenerates polyethylene terephthalate and gathers
The polymer or polypropylene terephthalate of propylene glycol ester terephthalate and gathering for polybutylene terephthalate (PBT)
Close object, then regeneration polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate
The polymer of ester three.
In the present invention, the polyester in the polymer substrate is preferably alkali soluble polyester.In the present invention, the alkali soluble
Property polyester preferably introduce polyethylene glycol and 1, the polyester molecule chain of 3- ethylene isophthalate -5- sulfonate monomers,
More preferably include poly- (terephthalic acid (TPA), 5-sodium sulfo isophthalate, ethylene glycol) copolyesters, poly- (terephthalic acid (TPA), isophthalic
Dioctyl phthalate -5- sodium sulfonates, ethylene glycol, 2- methyl-1s, 3-propanediol) copolyesters, poly- (terephthalic acid (TPA), M-phthalic acid -5- sulphurs
Sour sodium, ethylene glycol, 1,3-PD) copolyesters, poly- (terephthalic acid (TPA), 5-sodium sulfo isophthalate, butanediol) copolyesters
Or poly- (terephthalic acid (TPA), 5-sodium sulfo isophthalate, hexylene glycol) copolyesters.In the present invention, the alkali soluble polyester
The regularity of macromolecular is destroyed, and keeps it soluble in hot diluted alkaline water.
In the present invention, the fusing point of polyamide is preferably 110~180 DEG C in the polymer substrate, more preferably 120~
170 DEG C, most preferably 130~160 DEG C.
In the present invention, polyamide preferably includes PA6/PA66, PA6/PA66/PA12, PA6/ in the polymer substrate
The copolymer of one or more or several substances in PA66/PA610 and PA6/PA66/PA1010, more preferably PA6/
One kind in PA66, PA6/PA66/PA12, PA6/PA66/PA610 and PA6/PA66/PA1010, two kinds, three kinds or four kinds
The polymerization of the copolymer of mixture or two kinds, three kinds or four kinds substances, most preferably PA6/PA66 and PA6/PA66/PA12
Object either PA6/PA66/PA12 and PA6/PA66/PA610 polymer again or PA6/PA66, PA6/PA66/PA12 and
The polymer of PA6/PA66/PA610 three.
In the present invention, the polyamide is preferably conventional polyamide, and the fusing point of the conventional polyamide is preferably 210~
270 DEG C, more preferably 220~260 DEG C, most preferably 230~250 DEG C.
In the present invention, the conventional polyamide preferably includes PA6, PA66, one or more in PA11 and PA12, more
One kind in preferably PA6, PA66, PA11 and PA12, two kinds, the mixtures of three kinds or four kinds, most preferably PA6 and PA66's
Mixture either PA66 and PA12 mixture again or the mixture of PA6, PA66 and PA12 three.
In the present invention, in the polymer substrate mass ratio of normal polyester and low-melting point polyester be preferably (50~
90)：(50~10), more preferably (60~80)：(40~20).
In the present invention, the mass ratio of conventional polyamide and low melting point polyamide is preferably (50 in the polymer substrate
~90)：(50~10), more preferably (60~80)：(40~20).
In the present invention, alkali soluble polyester and the mass ratio of polyester or polyamide are preferably (30 in the polymer substrate
~70)：(70~30), more preferably (40~60)：(60~40).
In the present invention, the mass ratio of cortex Masterbatch and polymer substrate is preferably (0~10) in the cortex:(90
~100), more preferably (1~9):(91~99), most preferably (2~8):(92~98).
In invention, the mass ratio of the cortical material and sandwich layer substance is preferably (20~80):(80~20), more preferably
For (30~70):(70~30), most preferably (40~60):(60~40).
In the present invention, the diameter of the compound colored light catalysis fibre of the core-skin type is preferably 0.05~4000 μm, more excellent
It is selected as 200~3000 μm, most preferably 300~2000 μm.
In the present invention, it is fine to account for the compound colored light catalysis of core-skin type for the gross mass of the sandwich layer Masterbatch and cortex Masterbatch
The mass content of dimension is preferably 1%~6%, and more preferably 3%~4%.
In the present invention, the sandwich layer Masterbatch and cortex Masterbatch are preferably independently red master batch, blue master batch, Huang
The mixture of one or more of Masterbatch, black agglomerate, purple master batch, green master batch, orange master batch can be specifically
The mixture of red master batch, blue master batch, yellow masterbatch, one kind in black agglomerate, two kinds, three kinds or four kinds substances；More
Body such as red master batch and the blue mixture of master batch or the mixture of yellow masterbatch and black agglomerate.When the Masterbatch is
When mixture, the present invention does not have special restriction to the amount ratio of each Masterbatch, using the mixture of arbitrary proportion.
The present invention does not have particular/special requirement to the source of the Masterbatch, using commercial product well known to those skilled in the art
Or it is prepared according to this field conventional technical means.
The present invention also provides the preparation methods of the compound colored light catalysis fibre of core-skin type described in above-mentioned technical proposal, including
Following steps：
(1) it shapes, cool down, oil, after drafting forming through ejection successively after melting cortex raw material and core layer raw material respectively,
Cortex raw material and core layer raw material are wound, precursor is obtained；
(2) the partial polymer matrix in the precursor removal cortex obtained the step (1), exposes photochemical catalyst,
Obtain the compound colored light catalysis fibre of core-skin type.
The present invention shapes successively through ejection after melting cortex raw material and core layer raw material respectively, cools down, oils, drafting forming
Afterwards, obtained Cortical fiber is wound around core fibers, obtains precursor.In the present invention, cortex raw material in the precursor
Weight content is preferably 20~80%, more preferably 30~70%, most preferably 40~60%.
In the present invention, the mass ratio of the photochemical catalyst and precursor is preferably (0.5~10):(90~99.5), it is more excellent
It is selected as (2~8):(92~98), most preferably (4~6):(94~96).
In the present invention, the diameter of the precursor is preferably 0.1~5000 μm, more preferably 0.2~500 μm, most preferably
It is 0.4~100 μm.
The present invention shapes, cools down, oils to the ejection, the concrete mode of drafting forming and winding does not have special limit
It is fixed, using mode well known to those skilled in the art.
After obtaining precursor, the precursor is removed the partial polymer matrix in cortex by the present invention, and it is compound to obtain core-skin type
Coloured photocatalytic fiber.The present invention does not have particular/special requirement to the specific implementation mode of the removal partial polymer matrix, uses
Method well-known to those skilled in the art carries out.Present invention preferably uses alkali decrement treatments to remove in the cortex component
Partial polymer matrix.In the present invention, when containing alkali soluble polyester in the polymer substrate, the present invention is preferred
Alkali soluble polyester is completely removed.
In the present invention, the mass ratio of precursor 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 comprise sodium hydroxide,
Accelerating agent 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 accelerating agent 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 of ammonium chloride.In the present invention, concentration of the accelerating agent 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
It is selected as 75~85 DEG C；The time of the alkali decrement treatment is preferably 20~120min, more preferably 40~100min, most preferably
60~80min.
The present invention preferably washes the fiber that alkali decrement treatment obtains.The present invention is no to the washing special to be wanted
It asks, it can be by the fiber wash to neutrality.
After the washing, the present invention obtains the compound colored light catalysis of core-skin type to preferably washing product is dried
Fiber.In the present invention, the temperature of the drying is preferably 60~100 DEG C, more preferably 70~90 DEG C, most preferably 75~85
DEG C, the time of the drying is preferably 60min~300min, more preferably 90min~240min.
The present invention also provides the compound colored light catalysis fibre of core-skin type described in above-mentioned technical proposal or above-mentioned technical proposals
Application of the compound colored light catalysis fibre of core-skin type that the preparation method obtains in photocatalytic degradation.
In the present invention, the application is preferably included the compound colored light catalysis fibre of core-skin type for removing in waste water
Dyestuff.
It to compound colored light catalysis fibre of core-skin type provided by the invention and preparation method thereof and is answered with reference to embodiment
With being described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Take 45 parts of conventional polyethylene terephthalates (fusing point is 260 DEG C), 6 parts of red master batches and 49 parts of cortex components
Core-sheath spinning is carried out, core-sheath type colored fibre precursor is obtained, the low melting point that the cortex group is divided into 130 DEG C of fusing point is poly-
Ethylene glycol terephthalate and composite photo-catalyst (89% TiO2, 10.5% g-C3N4, 0.5% graphene), it is described
Skin quality ratio is 49%, and the mass ratio that catalyst accounts for fiber is 10%, and the core-sheath type colored fibre precursor is short fibre
Dimension shape, a diameter of 21 μm.
Then 50g core-sheath type colored fibre precursor is taken, is added into alkali decrement treatment liquid and handles 30min, it is described
The bath raio of alkali decrement treatment is 1:50, a concentration of 35g/L of sodium hydroxide, accelerating agent trimethyl bromination in treatment fluid
A concentration of 1g/L of ammonium, 100 DEG C of water temperature.Then it is washed to neutrality, is placed in 125 DEG C of baking ovens tiling drying to get to dissolving portion
Divide the coloured photocatalytic fiber of core-sheath type of cortex low melting point polyethylene terephthalate.
The coloured photocatalytic fiber of 40mg core-sheath types that the present invention obtains the present embodiment is under simulated solar irradiation to Asia
Methyl blue (a concentration of 2 × 10-5Mol/L photocatalytic degradation experiment) is carried out, experimental result is as described in Figure 1, and Fig. 1 obtains for the present embodiment
Photocatalytic activity figure of the coloured photocatalytic fiber of core-sheath type arrived to methylene blue.As shown in Figure 1, the present embodiment carries
The coloured photocatalytic fiber of core-sheath type of confession is very high for the degradation rate of methylene blue, can degrade at 40 minutes or so
All methylene blues.
Embodiment 2
Take 36 parts of regeneration polyethylene terephthalates (fusing point is 260 DEG C), 4 parts of yellow masterbatch and 60 parts of cortex components
Core-sheath spinning is carried out, core-sheath type colored fibre precursor is obtained.The low melting point that the cortex group is divided into 114 DEG C of fusing point is poly-
Succinic acid-butanediol ester and composite photo-catalyst (83% TiO2, 15% g-C3N4, 2% WO3), the skin quality ratio
It is 60%, the mass ratio that catalyst accounts for fiber is 10%, and the core-sheath type colored fibre precursor is that length is Filamentous, a diameter of 24
μm。
Then 100g core-sheath type colored fibre precursor is taken, is added into alkali decrement treatment liquid and handles 40min, it is described
The bath raio of alkali decrement treatment is 1:40, a concentration of 25g/L of sodium hydroxide, accelerating agent dodecyl dimethyl benzyl in treatment fluid
A concentration of 1g/L of ammonium chloride, 90 DEG C of water temperature.Then it is washed to neutrality, is placed in 100 DEG C of baking ovens tiling drying to get to dissolving
The coloured photocatalytic fiber of core-sheath type of partial thickness low melting point poly butylene succinate.
The present invention carries out the coloured photocatalytic fiber of core-sheath type that the present embodiment obtains in the way of embodiment 1
Detection, testing result show degrading activity of the coloured photocatalytic fiber of core-sheath type provided in this embodiment to methylene blue
Substantially it is consistent.
Embodiment 3
50 parts of routine PA6 (fusing point is 225 DEG C), 6 parts of blue master batches and 44 parts of cortex components are taken to carry out core-sheath spinning,
Obtain core-sheath type colored fibre precursor.The cortex group is divided into the low melting point polyethylene terephthalate of 120 DEG C of fusing point
Mixture and composite photo-catalyst (79% TiO of ester and poly butylene succinate2, 18% g-C3N4, 3% tetracarboxylic
ZnPc), the skin quality ratio is 44%, and the mass ratio that catalyst accounts for fiber is 10%, the coloured fibre of core-sheath type
Dimension precursor be staple fiber shape, a diameter of 21 μm.
Then 100g core-sheath colored fibre precursor is taken, is added into alkali decrement treatment liquid and handles 30min, the alkali
The bath raio of decrement treatment is 1:30, a concentration of 30g/L of sodium hydroxide, accelerating agent cetyl trimethylammonium bromide in treatment fluid
A concentration of 1g/L, 100 DEG C of water temperature.Then it is washed to neutrality, is placed in 115 DEG C of baking ovens tiling drying to get to dissolving part
The coloured photocatalysis of mixture core-sheath type of cortex low melting point polyethylene terephthalate and poly butylene succinate
Fiber.
The present invention carries out the coloured photocatalytic fiber of core-sheath type that the present embodiment obtains in the way of embodiment 1
Detection, testing result show degrading activity of the coloured photocatalytic fiber of core-sheath type provided in this embodiment to methylene blue
Substantially it is consistent.
Embodiment 4
Take 47 parts of conventional polyethylene terephthalates (fusing point is 255 DEG C), 4 parts of red master batches and 49 parts of cortex components
Core-sheath spinning is carried out, core-sheath type colored fibre precursor is obtained.The low melting point that the cortex group is divided into 125 DEG C of fusing point is poly-
Ester elastomer and composite photo-catalyst (75% TiO2, 23% g-C3N4, 2% tetranitro cobalt phthalocyanine), the skin quality
Than being 49%, the mass ratio that catalyst accounts for fiber is 10%, and the core-sheath type colored fibre precursor is staple fiber shape, diameter
It is 21 μm.
Then 100g core-sheath type colored fibre precursor is taken, is added into alkali decrement treatment liquid and handles 30min, it is described
The bath raio of alkali decrement treatment is 1:30, a concentration of 35g/L of sodium hydroxide, accelerating agent octadecyldimethyl hydroxyl second in treatment fluid
A concentration of 1g/L of base ammonium nitrate, 100 DEG C of water temperature.Then be washed to neutrality, be placed in 120 DEG C of baking ovens tiling drying to get to
Dissolve the coloured photocatalytic fiber of core-sheath type of partial thickness low-melting point polyester elastomer.
The present invention carries out the coloured photocatalytic fiber of core-sheath type that the present embodiment obtains in the way of embodiment 1
Detection, testing result show degrading activity of the coloured photocatalytic fiber of core-sheath type provided in this embodiment to methylene blue
Substantially it is consistent.
Embodiment 5
35 parts of conventional polypropylene terephthalate (fusing point is 228 DEG C) and 65 parts of cortex components are taken to carry out core-sheath
Spinning obtains core-sheath type colored fibre precursor.The cortex group is divided into the low melting point poly terephthalic acid second of 110 DEG C of fusing point
Diol ester and composite photo-catalyst (63% TiO2, 35% g-C3N4, 2% tetracarboxylic cobalt phthalocyanine), the skin quality ratio is
65%, catalyst account for fiber mass ratio be 10%, the core-sheath type colored fibre precursor be staple fiber shape, a diameter of 22
μm。
Then 100g core-sheath colored fibre precursor is taken, is added into alkali decrement treatment liquid and handles 30min, the alkali
The bath raio of decrement treatment is 1:40, a concentration of 35g/L of sodium hydroxide, accelerant N, N '-polyoxyethylene groups alkyl in treatment fluid
A concentration of 1g/L of benzyl ammonium chloride, 100 DEG C of water temperature.Then be washed to neutrality, be placed in 100 DEG C of baking ovens tiling drying to get
To the coloured photocatalytic fiber of core-sheath type for dissolving partial thickness polyethylene terephthalate.
The present invention carries out the coloured photocatalytic fiber of core-sheath type that the present embodiment obtains in the way of embodiment 1
Detection, testing result show degrading activity of the coloured photocatalytic fiber of core-sheath type provided in this embodiment to methylene blue
Substantially it is consistent.
As seen from the above embodiment, the present invention provides the sides that a kind of melt composite spinning prepares coloured photocatalytic fiber
Method.Present invention offer includes the core-sheath colored fibre of cortex component and sandwich layer component；The sandwich layer group be divided into normal polyester,
Masterbatch；The cortex component includes the blend, Masterbatch, light of polyester, polyamide, alkali soluble polyester and polyester or polyamide
Catalyst includes the following steps：After cortex component and sandwich layer component drying and melting, sprays and shapes by same composite component,
Then by cooling, oil, drafting forming, winding obtain the core-sheath type colored fibre precursor containing photochemical catalyst.Then
Remove polyester, polyamide, the alkali soluble polyester in partial thickness component so that the light inside core-sheath type colored fibre precursor
Catalyst is exposed, and obtains the coloured photocatalytic fiber of core-sheath type.The experimental results showed that core-sheath provided by the invention
The coloured photocatalytic fiber of type is very high for the degradation rate of methylene blue, and can degrade all methylene at 40 minutes or so
It is blue.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of compound colored light catalysis fibre of core-skin type, including cortex and sandwich layer, the sandwich layer include polyester and sandwich layer color masterbatch
Grain；The cortex includes polymer substrate, cortex Masterbatch and photochemical catalyst, and the polymer substrate includes polyester and/or gathers
Amide, the photochemical catalyst partial denudation is in cortical surface, and the photochemical catalyst dispersion is in the polymer matrix.
2. the compound colored light catalysis fibre of core-skin type according to claim 1, which is characterized in that the photochemical catalyst accounts for skin
The mass content of the compound colored light catalysis fibre of core pattern is 3%~14%；
The mass content that the total amount of the sandwich layer Masterbatch and cortex Masterbatch accounts for the compound colored light catalysis fibre of core-skin type is 1%
~6%.
3. the compound colored light catalysis fibre of core-skin type according to claim 1 or 2, which is characterized in that the photochemical catalyst
It is compound including titanium dioxide, titanium dioxide-graphene complex, class graphite phase carbon nitride, class graphite phase carbon nitride-graphene
Object, titanium dioxide-class graphite phase carbon nitride compound, titanium dioxide-tungstic acid compound ,-three oxygen of class graphite phase carbon nitride
Change tungsten compound, titanium dioxide-class graphite phase carbon nitride-tungstic acid compound, titanium dioxide-class graphite phase carbon nitride-gold
Belong to phthalocyanine compound, class graphite phase carbon nitride-metal phthalocyanine compound, titanium dioxide-metal phthalocyanine compound, metal phthalocyanine-
Tungstic acid compound, class graphite phase carbon nitride-tungstic acid-metal phthalocyanine compound and-three oxygen of titanium dioxide-metal phthalocyanine
Change one or more in tungsten compound.
4. the compound colored light catalysis fibre of core-skin type according to claim 1, which is characterized in that the sandwich layer center core layer color
The mass ratio of master batch and polyester is (1~10):(90~99).
5. the compound colored light catalysis fibre of core-skin type according to claim 1 or 4, which is characterized in that skin in the cortex
The mass ratio of layer Masterbatch and polymer substrate is (0~10):(90~100).
6. the compound colored light catalysis fibre of core-skin type according to claim 1, which is characterized in that the core-skin type is compounded with
A diameter of 0.05~4000 μm of coloured light catalysis fibre.
7. the preparation method of the compound colored light catalysis fibre of core-skin type described in claim 1~6 any one, including following step
Suddenly：
(1) it shapes, cool down, oil, after drafting forming through ejection successively after melting cortex raw material and core layer raw material respectively, will
The Cortical fiber arrived is wound around core fibers, obtains precursor；
(2) the partial polymer matrix in the precursor removal cortex obtained the step (1), exposes photochemical catalyst, obtains
The compound colored light catalysis fibre of core-skin type.
8. preparation method according to claim 7, which is characterized in that the weight content of cortex raw material is 20 in the precursor
~80%.
9. preparation method according to claim 7, which is characterized in that a diameter of 0.1~5000 μm of the precursor.
10. the compound colored light catalysis fibre of core-skin type described in claim 1~6 any one or claim 7~9 any one
Application of the compound colored light catalysis fibre of core-skin type that the preparation method obtains in photocatalytic degradation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810584259.3A CN108728933A (en) | 2018-06-06 | 2018-06-06 | A kind of compound colored light catalysis fibre of core-skin type and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810584259.3A CN108728933A (en) | 2018-06-06 | 2018-06-06 | A kind of compound colored light catalysis fibre of core-skin type and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108728933A true CN108728933A (en) | 2018-11-02 |
Family
ID=63932425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810584259.3A Pending CN108728933A (en) | 2018-06-06 | 2018-06-06 | A kind of compound colored light catalysis fibre of core-skin type and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108728933A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110387600A (en) * | 2019-07-22 | 2019-10-29 | 海西纺织新材料工业技术晋江研究院 | It inhales acid and inhales alkali core-skin composite fiber and preparation method thereof |
| CN110835801A (en) * | 2019-11-15 | 2020-02-25 | 福建汇龙化纤纺织实业有限公司 | Nano metal antibacterial fiber fabric and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11269759A (en) * | 1998-03-20 | 1999-10-05 | Teijin Ltd | Treatment of polyester fiber |
| CN201406488Y (en) * | 2009-04-30 | 2010-02-17 | 江苏江南高纤股份有限公司 | Skin core type color fiber |
| CN104846467A (en) * | 2015-05-20 | 2015-08-19 | 江苏腾盛纺织科技集团有限公司 | Dacron color silk with photocatalytic degradation function and preparing method thereof |
| CN106319673A (en) * | 2016-08-19 | 2017-01-11 | 浙江理工大学 | Composite photocatalytic fibers and preparation method thereof |
| CN106311347A (en) * | 2016-08-19 | 2017-01-11 | 浙江理工大学 | Sheath-core composite photocatalytic fiber and method for preparing same |
-
2018
- 2018-06-06 CN CN201810584259.3A patent/CN108728933A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11269759A (en) * | 1998-03-20 | 1999-10-05 | Teijin Ltd | Treatment of polyester fiber |
| CN201406488Y (en) * | 2009-04-30 | 2010-02-17 | 江苏江南高纤股份有限公司 | Skin core type color fiber |
| CN104846467A (en) * | 2015-05-20 | 2015-08-19 | 江苏腾盛纺织科技集团有限公司 | Dacron color silk with photocatalytic degradation function and preparing method thereof |
| CN106319673A (en) * | 2016-08-19 | 2017-01-11 | 浙江理工大学 | Composite photocatalytic fibers and preparation method thereof |
| CN106311347A (en) * | 2016-08-19 | 2017-01-11 | 浙江理工大学 | Sheath-core composite photocatalytic fiber and method for preparing same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110387600A (en) * | 2019-07-22 | 2019-10-29 | 海西纺织新材料工业技术晋江研究院 | It inhales acid and inhales alkali core-skin composite fiber and preparation method thereof |
| CN110387600B (en) * | 2019-07-22 | 2021-10-26 | 海西纺织新材料工业技术晋江研究院 | Acid and alkali absorption sheath-core composite fiber and preparation method thereof |
| CN110835801A (en) * | 2019-11-15 | 2020-02-25 | 福建汇龙化纤纺织实业有限公司 | Nano metal antibacterial fiber fabric and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108691031A (en) | A kind of core-skin type composite photocatalyst fiber and its preparation method and application | |
| CN106319673B (en) | A kind of composite photocatalyst fiber and preparation method thereof | |
| CN107326468B (en) | A kind of porous photocatalytic fiber and preparation method thereof | |
| CN106311347A (en) | Sheath-core composite photocatalytic fiber and method for preparing same | |
| CN108823672A (en) | A kind of coloured photocatalytic fiber and preparation method thereof | |
| CN103046151B (en) | Graphene blend regenerated cellulose fiber and preparation method thereof | |
| CN108728933A (en) | A kind of compound colored light catalysis fibre of core-skin type and its preparation method and application | |
| CN204434966U (en) | A kind of suction look device | |
| CN102373515B (en) | TiO2-SiO2 bi-component nano-grade fiber and preparation method thereof | |
| CN109706544A (en) | A kind of coloured catalysis composite antibacterial fibre and its preparation method and application | |
| CN109759114A (en) | A kind of g-C3N4/TiO2/ RGO three-dimensional Z-type photochemical catalyst and its electro spinning method for preparing in situ | |
| CN106319672B (en) | A kind of photocatalytic fiber and preparation method thereof | |
| CN103194886A (en) | Preparation method of multi-phase heterogeneous visible light catalysis functional fabric | |
| CN107583654A (en) | The preparation method of nanoporous microballoon with adsorption photochemical catalysis synergy | |
| CN106423295B (en) | A kind of photochemical catalyst and its preparation method and application | |
| CN108677271A (en) | A kind of colour superfine photocatalytic fiber and preparation method thereof | |
| CN109402774A (en) | A kind of anti-fibrillated cellulose fibers and preparation method thereof | |
| CN107723831A (en) | A kind of original liquid coloring polyester fiber and preparation method thereof | |
| CN108855234A (en) | A kind of method that energy light degradation dyestuff microfluid prepares Ag-carried nanometer titanium dioxide PVP fiber | |
| CN108889318A (en) | Composite photocatalyst material of Degradation Formaldehyde and preparation method thereof | |
| CN106311348A (en) | Composite photocatalyst, and preparation method and application thereof | |
| CN102517887B (en) | Method for preparing silicon protective in-situ deposition photocatalytic functional textile | |
| CN111441102B (en) | Preparation method of antiviral composite polyester fiber | |
| CN104923277A (en) | Ta3N5/Bi2WO6 heterojunction fiber photo-catalyst and preparation method therefor | |
| CN104888833B (en) | A kind of Ta3N5/ C composite fibre photochemical catalysts and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181102 |
|
| RJ01 | Rejection of invention patent application after publication |