CN109112661A - The preparation method of spinning technique and titanium dioxide powder containing dioxide composite titanium valve - Google Patents
The preparation method of spinning technique and titanium dioxide powder containing dioxide composite titanium valve Download PDFInfo
- Publication number
- CN109112661A CN109112661A CN201810711541.3A CN201810711541A CN109112661A CN 109112661 A CN109112661 A CN 109112661A CN 201810711541 A CN201810711541 A CN 201810711541A CN 109112661 A CN109112661 A CN 109112661A
- Authority
- CN
- China
- Prior art keywords
- composite titanium
- solution
- dioxide
- titanium valve
- spinning
- 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 44
- 239000010936 titanium Substances 0.000 title claims abstract description 44
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 42
- 238000009987 spinning Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000843 powder Substances 0.000 title claims abstract description 13
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 12
- -1 silver Chemical class 0.000 claims abstract description 8
- 239000004744 fabric Substances 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000000126 substance Substances 0.000 claims description 20
- 125000003368 amide group Chemical group 0.000 claims description 18
- 229920000587 hyperbranched polymer Polymers 0.000 claims description 18
- 229910052737 gold Inorganic materials 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 241000790917 Dioxys <bee> Species 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000002074 melt spinning Methods 0.000 claims description 3
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 229910052709 silver Inorganic materials 0.000 abstract description 5
- 239000004332 silver Substances 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 3
- 230000000845 anti-microbial effect Effects 0.000 abstract description 2
- 230000004044 response Effects 0.000 abstract description 2
- 230000003595 spectral effect Effects 0.000 abstract description 2
- 239000010931 gold Substances 0.000 description 23
- 239000002245 particle Substances 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 13
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000008187 granular material Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011943 nanocatalyst Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- YYAPGCGSUOZSNQ-UHFFFAOYSA-K ethanol;trichlorogold Chemical compound CCO.Cl[Au](Cl)Cl YYAPGCGSUOZSNQ-UHFFFAOYSA-K 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910014291 N—Cu Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
-
- 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
- D01F1/103—Agents inhibiting growth of microorganisms
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses the preparation methods of a kind of spinning technique containing dioxide composite titanium valve and titanium dioxide powder, comprising the following steps: spinning master batch is carried out porous processing, makes to form hole on master batch, and the mean inside diameter of hole are as follows: 50nm-20 μm；Step (1) treated master batch is mixed with dioxide composite titanium valve, enter the dioxide composite titanium valve in the hole of the master batch, the dioxide composite titanium valve is N-Au codope composite titanium dioxide or N-Ag codope composite titanium dioxide；Using be mixed with composite titanium dioxide receive powder master batch carry out spinning.The metals such as silver, which are added, can expand light absorbing spectral region, and fabric is made to have good response effect under sunlight.The fiber and fabric obtained through spinning has anti-microbial property and antistatic property.
Description
Technical field
The present invention relates to a kind of preparation method of catalysis material, in particular to a kind of corresponding, height with high visible is urged
Change the light-catalysed preparation method of dioxide composite titanium valve of the multi-element doping of efficiency and adulterates the spinning of the dioxide composite titanium valve
Silk technique.
Background technique
Nano-titanium dioxide has high catalytic activity, good as important inorganic transition metal oxide material
Against weather, excellent anti-uv-ray.In recent years, the research of titanium dioxide nano material is growing day by day, at waste water
Concern of the fields such as reason, sun-proof skin care, coating and sensor, photochemical catalyst by people.Compared to other transition metal oxides,
Nano-titanium dioxide can absorb ultraviolet light, reflection ultraviolet light, can also be through visible light, before being superior performance, great development
The ultra-violet protecting agent on way.But there is also some shortcomings as catalyst for pure nano-titanium dioxide semiconductor material: being certainly first
The forbidden bandwidth of body is wider (Eg=3.2ev), is only capable of the ultraviolet light that absorbing wavelength is less than 387nm, and most to accounting in sunlight
Several visible lights does not generate effect；The recombination probability of followed by electron-hole is big, and the effective photon time-to-live is short, quantity is few,
So that nano-titanium dioxide can not give full play to its catalytic.
In order to improve nano-titanium dioxide in the application of photocatalysis field, a large amount of report displays, to nano-titanium dioxide into
Row doping is a kind of effective ways to the absorption of visible light to reduce its forbidden bandwidth or improve.Doping method is related to metal and non-
Metal-doped, ion doping, semiconductors coupling and surface modification etc., wherein precious metal doping effect is best, and doping approach includes
Ultraviolet photoreduction met hod, chemical reduction method and electrochemical deposition method etc..After nano-titanium dioxide light excitation after modification, valence band
The electronics of middle generation flows to the lower metal of Fermi's energy, so that the separation of light induced electron and hole, improves quantum efficiency, in turn
Improve the photocatalysis performance of nano-titanium dioxide.Common metal is doped with Pt, Ag, Pd and various rare metals, metal ion
And metal oxide, but it is metal-doped still lower to the utilization rate of visible light.Based on nonmetal doping is mainly adulterated with N, but N
Doping also easily causes the compound of electrons and holes, reduces photocatalysis efficiency.Therefore, metal and nonmetallic co-doped are utilized
Titanium dioxide granule can act synergistically, and while effectively expanding visible light region, improve photocatalysis efficiency, preparation can be wide
The catalysis material of general application.
The photocatalysis performance of nano-titanium dioxide and its form have very big relationship, at present its existence form have spherical shape, stick,
It is linear etc..The preparation method of titania nanoparticles includes sol-gel method, microemulsion method, solvent method and hydro-thermal reaction
Method usually first prepares titanium dioxide granule, then titanium dioxide granule is made through hydro-thermal.Nano-silica made from these methods
Change titanium particle size, size distribution and reaction condition directly affect titanium dioxide granule surface topography and size it is equal
One property, and the energy consumption of this two-step synthesis method is higher, seriously polluted, does not meet low energy consumption, " green " production requirement.
The photocatalytic of modified nano-titanium dioxide is also related with the state of dopant, structure, content, distribution etc..Such as mix
When miscellaneous metal simple-substance, especially golden simple substance, shadow of the golden simple substance catalytic activity by nanogold particle size, load capacity etc.
It rings.Studies have shown that showing higher catalytic activity as gold particle size < 10nm；When golden simple substance load capacity < 5%, compared with
It is easy to get the gold particle of small size.In addition, the specific surface area of nano-titanium dioxide and with the interaction of gold particle also shadow
Ring the activity for arriving composite catalyst.When load capacity is excessive, the compound of electrons and holes is accelerated instead, reduces catalytic efficiency.It is comprehensive
On, during loaded metal particle, the size of metallic particles and the controlled distribution on nano-titanium dioxide seem
It is particularly important.In addition, process time is shortened using simple, convenience and high-efficiency preparation process, save the cost and WeiLai Technology
Developing direction.
Alkali decrement treatment is that polyethylene terephthalate and its derivative are handled in high temperature and denseer caustic lye of soda
Process, by after alkaline etching, quality mitigates on surface, and surface forms pit, and increases the hole on treated object surface.
Summary of the invention
The purpose of the present invention is to overcome the deficiency in the prior art, provides a kind of simple process, is able to achieve with more excellent compound
The spinning technique of titanium dioxide homogeneous blend, and preparation N-Au or/and N-Ag codope composite titanium dioxide.Pass through the party
The titanium dioxide powder of the codopes such as the N-Au or/and N-Ag of method preparation has antibacterial, uvioresistant, high catalytic activity and environmentally friendly nothing
The advantage of pollution can be widely applied to weaving, gas purification, sewage treatment and solar battery etc..
The first technical solution of the invention are as follows: a kind of spinning technique containing dioxide composite titanium valve, including following step
It is rapid:
(1) spinning master batch is subjected to porous processing, makes to form hole on master batch, and the mean inside diameter of hole are as follows: 50nm-
20μm；
(2) step (1) treated master batch is mixed with dioxide composite titanium valve, enters the dioxide composite titanium valve
Into the hole of the master batch, the dioxide composite titanium valve is that N-Au codope composite titanium dioxide or N-Ag codope are compound
Titanium dioxide；
(3) using be mixed with composite titanium dioxide receive powder master batch carry out spinning.
Further, the master batch material is polyethylene terephthalate and its derivative, the porous processing
It is the process that master batch is impregnated to reaction in the lye of certain temperature.How the immersion treatment in lye is at Alkali reduction to above-mentioned master batch
It manages, the reaction temperature in treatment process is preferably shorter than the glass transition temperature of polyethylene terephthalate and its derivative.
Further, the dioxide composite titanium valve is the metal co-doped dioxide composite titanium valve of N-.
Further, the N- metal are as follows: one of N-Au, N-Ag, N-Pt, N-Cu or a variety of.
Further, the spinning is melt spinning.
A kind of second of technical solution of the invention are as follows: preparation method of dioxide composite titanium valve, comprising the following steps:
(a) solution of tetrabutyl titanate is added in acid solution, stirring is converted into spawn, i.e. dioxy after standing
Change titanium gel；
(b) solution of solution and Hyperbranched Polymer with Terminal Amido containing golden simple substance or silver-colored simple substance is mixed；
(c) mixed solution that the titania gel that step (a) obtains is obtained with step (b) is sufficiently mixed, and kept
A period of time within the temperature range of 180~240 DEG C；It is drying to obtain the dioxide composite titanium valve of N-Au or N-Ag codope.
A kind of the third technical solution of the invention are as follows: system of dioxide composite titanium valve as stated in claim 1 or 2
Preparation Method, which comprises the following steps:
(I) solution of tetrabutyl titanate is added in acid solution, stirring is converted into spawn, i.e. dioxy after standing
Change titanium gel；
(II) chlorauric acid solution or silver nitrate are added in the solution of dissaving polymer, and ebuillition of heated；
(III) solution containing golden simple substance or silver-colored simple substance in step (II) is added to the molten of Hyperbranched Polymer with Terminal Amido
In liquid, and it is uniformly mixed；
(IV) mixed solution that the titania gel that step (I) obtains is obtained with step (III) is sufficiently mixed, and protected
Hold a period of time within the temperature range of 180~240 DEG C；Then alcohol is washed, is washed, drying to get N-Au or N-Ag codope
Dioxide composite titanium valve.
Further, the concentration of the solution of tetrabutyl titanate is 50~150g/L.
Further, the Hyperbranched Polymer with Terminal Amido solution concentration is 10~100g/L.
Further, the mass ratio of the titania gel and mixed solution is 1:5~1:10.
4th kind of technical solution of the invention are as follows: a kind of use is prepared containing the spinning technique of dioxide composite titanium valve
Fiber, including contain fabric made of dioxide composite titanium valve spinning fibre and the spinning fibre.
Hyperbranched Polymer with Terminal Amido is that one kind has the spheroidal porous three-dimensional reticular structure of class, possesses a large amount of active ammonias
Base, highly dissoluble, highly viscous polymer.The polymeric inner has a large amount of gaps, may act as a nanometer reaction vessel control granule
Diameter and the nano particle for stablizing pattern are formed.
Reduction gold chloride, nitrate ion etc. can be complexed using Hyperbranched Polymer with Terminal Amido in the present invention, while controlling two
The principle of the growth of titan oxide particles.In hydro-thermal boiling part, amino in Hyperbranched Polymer with Terminal Amido is by metal ion
Be reduced into metal simple-substance, meanwhile, its tridimensional network by the stable dispersion of metal simple-substance in the solution.Amine-terminated hyperbrancedization
The special construction of polymer provides the effect of nanometer reaction vessel, controls the formation ruler of metal simple-substance and titanium dioxide granule
It is very little.In the high temperature process, amino abundant can be permeated to nano-titanium dioxide intracell, form N doping.By hydrothermal high-temperature
Process, golden simple substance or silver-colored simple substance, which are adhered on titanium dioxide granule by hydrogen bond action, and then obtain N-Au or N-Au etc., to be co-doped with
Miscellaneous composite titanium dioxide particle.
Compared with prior art, present invention has the advantage that (1) passes through the controllable acquisition of Hyperbranched Polymer with Terminal Amido
With composite titanium dioxide particle powder；(2) preparation process is simple, and metal list (preferably golden simple substance and silver-colored simple substance) matter size can
Control is conducive to improve production efficiency, save the cost；(3) poly- with amine-terminated hyperbrancedization respectively by adjusting gold chloride or silver nitrate
The concentration for closing object compares the size for the nanogold particle that can be effectively controlled；(4) nanogold particle adulterated divides on the titanium dioxide
Cloth is uniform, can preferably apply in every field；(5) using by composite titanium dioxide it is blended enter spinning master batch in by the way of, can
To allow composite titanium dioxide to be embedded in spinning fibre, guarantee that mixed titanium dioxide powder particles will not be because of washing in fiber
Etc. reasons fall off from fiber, and hybrid mode can make the distribution of composite titanium dioxide in the fibre more uniform；(6) it uses
Alkali decrement treatment spinning master batch, allows master batch to form porous structure, and such dioxide composite titanium powder can be entered deeply
In the hole of master batch, composite titanium dioxide powder particle is just uniformly mixed with master batch substantially before guaranteeing spinning molten, after overcoming
The stirring of road melting process is difficult to reach uniformly mixed problem.(7) light absorbing spectral region can be expanded by the metals such as silver being added,
Make fabric that there is good response effect under sunlight.The fiber and fabric obtained through spinning has anti-microbial property and antistatic
Performance.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples；
Fig. 1 is N-Au codope titanium dioxide particle transmission electron microscope picture prepared by embodiment 5；
Fig. 2 is N-Au codope titanium dioxide particle XRD spectrum prepared by embodiment 5.
Specific embodiment
In order to clarify the technical solutions and technical objectives of the present invention, with reference to the accompanying drawing and specific embodiment is the present invention
It is further to introduce.
Embodiment 1:
The porous processing that polyethylene terephthalate or derivatives thereof spinning master batch is carried out to Alkali reduction, makes master batch
Upper formation hole, and obtain the mean inside diameter of hole are as follows: 50nm-20 μm；It then will treated master batch and composite titanium dioxide
Powder mixing, enters dioxide composite titanium valve in the hole of master batch, and dioxide composite titanium valve is the compound dioxy of N-Au codope
Change titanium or N-Ag codope composite titanium dioxide；Finally using be mixed with composite titanium dioxide receive powder master batch carry out melt spinning
To obtain the final product.Wherein dioxide composite titanium valve is the dioxide composite titanium valve of N-Au or N-Ag codope.
Embodiment 2:
By 80ml concentration be 125g/L butyl titanate ethanol solution be added dropwise to by 10ml formic acid and 10ml go from
In the mixed solution of sub- water composition, and it is stirred continuously to solution and is light blue color.It is still aging until colloidal sol be in gel.It will
The gold chloride ethanol solution that 0.5ml concentration is 0.1mol/L is added to the Hyperbranched Polymer with Terminal Amido that 10ml concentration is 30g/L
Aqueous solution in, ebuillition of heated to solution be in pale pink.By the ethyl alcohol for the Hyperbranched Polymer with Terminal Amido that 50ml concentration is 60g/L
Solution is mixed to join in the solution, addition 10g titania gel after mixing is continued stirring until, using cell disruptor
It is put into ptfe autoclave, is heated 8 hours at 200 DEG C after mixing.After cooling, by solution ethanol washing three
Secondary, centrifugation, deionized water is washed three times, is centrifuged, and it is 26.5nm that average grain diameter just can be obtained after dry, and gold content is
1.2680%, gold particle diameter is the composite titanium dioxide nanocatalyst of the N-Au codope of 10.9nm.
Embodiment 3:
By 80ml concentration be 125g/L butyl titanate ethanol solution be added dropwise to by 10ml formic acid and 10ml go from
In the mixed solution of sub- water composition, and it is stirred continuously to solution and is light blue color.It is still aging until colloidal sol be in gel.It will
The silver nitrate aqueous solution that 0.30ml concentration is 0.1mol/L is added to the Hyperbranched Polymer with Terminal Amido that 10ml concentration is 50g/L
In aqueous solution, ebuillition of heated to solution is in glassy yellow.The ethyl alcohol for the Hyperbranched Polymer with Terminal Amido that 30ml concentration is 15g/L is molten
Liquid is mixed to join in the solution, continues stirring until addition 10g titania gel after mixing, mixed using cell disruptor
It is put into ptfe autoclave after closing uniformly, is heated 10 hours at 200 DEG C.After cooling, solution with ethanol washing three times,
Centrifugation, deionized water are washed three times, are centrifuged, and it is 33.1nm that average grain diameter just can be obtained after dry, and silver content is
0.8911%, Argent grain diameter is the composite titanium dioxide nanocatalyst of the N-Au codope of 6.6nm.
Embodiment 4:
The butyl titanate ethanol solution that 88ml concentration is 90g/L is added dropwise to by 15ml formic acid and 10ml deionization
In the mixed solution of water composition, and it is stirred continuously to solution and is light blue color.It is still aging until colloidal sol be in gel.By 0.30ml
The gold chloride ethanol solution that concentration is 0.2mol/L is added to the water-soluble of the Hyperbranched Polymer with Terminal Amido that 10ml concentration is 80g/L
In liquid, ebuillition of heated to solution is in pale pink.The ethanol solution for the Hyperbranched Polymer with Terminal Amido that 50ml concentration is 15g/L is mixed
Conjunction is added in the solution, continues stirring until addition 15g titania gel after mixing, is mixed using cell disruptor equal
It is put into ptfe autoclave after even, is heated 6 hours at 230 DEG C.After cooling, solution three times, is centrifuged with ethanol washing,
Deionized water is washed three times, centrifugation, and it is 35.7nm, gold content 1.0273%, gold that average grain diameter just can be obtained after dry
Particle diameter is the composite titanium dioxide nanocatalyst of the N-Au codope of 6.7nm.
Embodiment 5:
The butyl titanate ethanol solution that 86ml concentration is 70g/L is added dropwise to by 18ml formic acid and 10ml deionization
In the mixed solution of water composition, and it is stirred continuously to solution and is light blue color.It is still aging until colloidal sol be in gel.By 0.30ml
The silver nitrate aqueous solution that concentration is 0.08mol/L is added to the water-soluble of the Hyperbranched Polymer with Terminal Amido that 10ml concentration is 50g/L
In liquid, ebuillition of heated to solution is in glassy yellow.By the ethanol solution for the Hyperbranched Polymer with Terminal Amido that 550ml concentration is 18g/L
It is mixed to join in the solution, continues stirring until addition 8g titania gel after mixing, mixed using cell disruptor
It is put into ptfe autoclave after uniformly, is heated 14 hours at 220 DEG C.After cooling, solution with ethanol washing three times, from
The heart, deionized water are washed three times, centrifugation, and it is 20.5nm that average grain diameter just can be obtained after dry, silver content 1.6037%,
Argent grain diameter is the composite titanium dioxide nanocatalyst of the N-Ag codope of 6.2nm.
By taking embodiment 5 as an example, Fig. 1 is the transmission electron microscope picture for the dioxide composite titanium nano particle that embodiment 5 obtains, from figure
In, it is evident that titania nanoparticles become second nature good, uniform, partial size 20nm or so, many particles of surface doping.Comparative diagram
2 XRD spectrum, ten diffraction maximums respectively correspond the crystallographic plane diffraction peak (101) for anatase-type nanometer titanium dioxide, (004),
(200), (105), (211) and (204), and (111), (200), (220) and (311) are the crystallographic plane diffraction peak of Au simple substance, are brought into
Scherrer formula, is computed and obtains, the average-size of gold particle is 6.2nm.This result is consistent with transmission electron microscope observed result.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (10)
1. a kind of spinning technique containing dioxide composite titanium valve, which comprises the following steps:
(1) spinning master batch is subjected to porous processing, makes to form hole on master batch, and the mean inside diameter of hole are as follows: 50nm-20 μ
m；
(2) step (1) treated master batch is mixed with dioxide composite titanium valve, the dioxide composite titanium valve is made to enter institute
It states in the hole of master batch, the dioxide composite titanium valve is N-Au codope composite titanium dioxide or the compound dioxy of N-Ag codope
Change titanium；
(3) using be mixed with composite titanium dioxide receive powder master batch carry out spinning.
2. the spinning technique according to claim 1 containing dioxide composite titanium valve, it is characterised in that: the master batch material
For polyethylene terephthalate and its derivative, the porous processing is to impregnate master batch in the lye of certain temperature
The process of reaction.
3. the spinning technique according to claim 1 containing dioxide composite titanium valve, it is characterised in that: the compound dioxy
Changing titanium valve is the metal co-doped dioxide composite titanium valve of N-.
4. the spinning technique according to claim 1 containing dioxide composite titanium valve, it is characterised in that: the spinning is molten
Melt spinning.
5. a kind of preparation method of dioxide composite titanium valve as stated in claim 1 or 2, which is characterized in that including following
Step:
(a) solution of tetrabutyl titanate is added in acid solution, stirring is converted into spawn, i.e. titanium dioxide after standing
Gel；
(b) solution of solution and Hyperbranched Polymer with Terminal Amido containing golden simple substance or silver-colored simple substance is mixed；
(c) mixed solution that the titania gel that step (a) obtains is obtained with step (b) is sufficiently mixed, and is maintained at 180
A period of time within the temperature range of~240 DEG C；It is drying to obtain the dioxide composite titanium valve of N-Au or N-Ag codope.
6. a kind of preparation method of dioxide composite titanium valve as stated in claim 1 or 2, which is characterized in that including following
Step:
(I) solution of tetrabutyl titanate is added in acid solution, stirring is converted into spawn, i.e. titanium dioxide after standing
Gel；
(II) chlorauric acid solution or silver nitrate are added in the solution of dissaving polymer, and ebuillition of heated；
(III) solution containing golden simple substance or silver-colored simple substance in step (II) is added in the solution of Hyperbranched Polymer with Terminal Amido,
And it is uniformly mixed；
(IV) mixed solution that the titania gel that step (I) obtains is obtained with step (III) is sufficiently mixed, and be maintained at
A period of time within the temperature range of 180~240 DEG C；Then alcohol is washed, is washed, drying to get the compound of N-Au or N-Ag codope
Titanium dioxide powder.
7. preparation method according to claim 5 or 6, it is characterised in that: the concentration of the solution of tetrabutyl titanate is 50
~150g/L.
8. preparation method according to claim 5 or 6, it is characterised in that: the Hyperbranched Polymer with Terminal Amido solution is dense
Degree is 10~100g/L.
9. preparation method according to claim 5 or 6, it is characterised in that: the titania gel and mixed solution
Mass ratio is 1:5~1:10.
10. a kind of fibre that the spinning technique using as claimed in claim 1 or 2 containing dioxide composite titanium valve is prepared
Dimension, which is characterized in that including containing fabric made of dioxide composite titanium valve spinning fibre and the spinning fibre.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810711541.3A CN109112661A (en) | 2018-07-03 | 2018-07-03 | The preparation method of spinning technique and titanium dioxide powder containing dioxide composite titanium valve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810711541.3A CN109112661A (en) | 2018-07-03 | 2018-07-03 | The preparation method of spinning technique and titanium dioxide powder containing dioxide composite titanium valve |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109112661A true CN109112661A (en) | 2019-01-01 |
Family
ID=64822507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810711541.3A Pending CN109112661A (en) | 2018-07-03 | 2018-07-03 | The preparation method of spinning technique and titanium dioxide powder containing dioxide composite titanium valve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109112661A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004169267A (en) * | 1994-08-31 | 2004-06-17 | Kuraray Co Ltd | Hyperbaric, high strength conjugate fiber and method for producing the same |
| CN107537543A (en) * | 2017-09-11 | 2018-01-05 | 南通纺织丝绸产业技术研究院 | A kind of preparation method of N Au Ag coblended nano TiO 2 light catalysts |
| CN108060468A (en) * | 2018-01-12 | 2018-05-22 | 浙江东太新材料有限公司 | A kind of fused mass directly spinning preparation method of delustring PET fiber |
-
2018
- 2018-07-03 CN CN201810711541.3A patent/CN109112661A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004169267A (en) * | 1994-08-31 | 2004-06-17 | Kuraray Co Ltd | Hyperbaric, high strength conjugate fiber and method for producing the same |
| CN107537543A (en) * | 2017-09-11 | 2018-01-05 | 南通纺织丝绸产业技术研究院 | A kind of preparation method of N Au Ag coblended nano TiO 2 light catalysts |
| CN108060468A (en) * | 2018-01-12 | 2018-05-22 | 浙江东太新材料有限公司 | A kind of fused mass directly spinning preparation method of delustring PET fiber |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102350346B (en) | Preparation method of visible light catalyst with surface plasmon effect and application thereof | |
| CN101116808B (en) | Photocatalysis powder having a negative ion releasing function and method for preparing the same | |
| CN106732527B (en) | A kind of bismuth/composite bismuth vanadium photocatalyst and preparation method thereof and the application in photocatalytic degradation of organic matter | |
| CN103691433B (en) | A kind of Ag doped Ti O 2material, and its preparation method and application | |
| CN103172030A (en) | Oxide powder and preparation method thereof as well as catalyst and carrier thereof | |
| CN110227453B (en) | Preparation method of AgCl/ZnO/GO composite visible light catalyst | |
| Prabhu et al. | Synthesis, surface acidity and photocatalytic activity of WO3/TiO2 nanocomposites–an overview | |
| CN103721700B (en) | A kind of high activity SnO 2-TiO 2the preparation method of composite photo-catalyst | |
| CN109675607A (en) | Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material | |
| CN104801325A (en) | Photocatalyst composite structure and preparation method thereof | |
| She et al. | Spatially separated bimetallic cocatalysts on hollow-structured TiO 2 for photocatalytic hydrogen generation | |
| CN103816897B (en) | Titanium dioxide-Yin complex nucleus shell structure ball and its production and use | |
| CN105540640A (en) | Preparation method of flower-shaped nanometer zinc oxide | |
| CN106362742A (en) | Ag/ZnO nano-composite, preparation method thereof and application of composite | |
| CN110368942A (en) | The preparation method of transient metal doped titanium dioxide composite aerogel | |
| CN105521809A (en) | Preparation method of Cu:ZnO/N:rGO composite photocatalyst | |
| CN107497455B (en) | A kind of preparation method and applications of the ultra-thin Bismuth tungstate nano-sheet photochemical catalyst of Determination of Trace Sulfur surface modification | |
| CN111036246A (en) | Composite photocatalytic material and preparation method and application thereof | |
| CN106693996A (en) | Preparation method and application for bismuth sulfide-bismuth ferrate composite visible-light photocatalyst | |
| CN111054419B (en) | For CO 2 Reduced semiconductor/g-C 3 N 4 Photocatalyst and preparation method thereof | |
| Zhang et al. | Fabrication and study of a novel TiO2/g-C3N5 material and photocatalytic properties using methylene blue and tetracycline under visible light | |
| CN106362768B (en) | A kind of honeycomb ceramic plate loads TiO2The preparation technology of the immobilized photochemical catalysts of-NCP | |
| Lv et al. | Enhanced photocatalytic performance of hollow spherical CdS QDs@ ZrO2–TiO2 composites with double Z-scheme heterostructures | |
| CN105817241A (en) | Method for preparing copper phosphotungstate@titanium dioxide core-shell structured nanomaterial | |
| CN105749908A (en) | Photocatalyst of Au@TiO2 hollow core-shell structure and preparation method of photocatalyst of Au@TiO2 hollow core-shell structure |
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 |