CN108914250B - Preparation method of polyacetylacetonato titanium precursor sol spinning solution, titanium oxide continuous fiber and nano fiber - Google Patents
Preparation method of polyacetylacetonato titanium precursor sol spinning solution, titanium oxide continuous fiber and nano fiber Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/04—Dry spinning methods
Abstract
The invention relates to a preparation method of a polyacetylacetonato titanium precursor sol spinning solution, titanium oxide continuous fibers and nano fibers. The method takes tetrabutyl titanate as a titanium source to synthesize a titanium polyacetylacetonate precursor, uniformly mixes the precursor, an auxiliary agent and a solvent according to a certain proportion to obtain a sol spinning solution, respectively obtains precursor nano fibers and continuous fibers by electrostatic spinning and dry spinning, and obtains titanium oxide nano fibers and continuous fibers by heat treatment. The diameter of the prepared titanium oxide nanofiber is 400-1200 nm, and the length of the prepared titanium oxide nanofiber is 2-6 cm; the diameter of the prepared titanium oxide continuous fiber is 20-100 μm, the length is more than tens of meters, and the strength is 100 MPa-1.0 GPa. The method has the advantages of simple process, low cost, capability of avoiding the existence of impurity ions, good spinnability of the prepared precursor sol, stability, difficult gelation, high strength of the prepared fiber and good catalytic performance.
Description
Technical Field
The invention relates to a preparation method of a polyacetylacetonato titanium precursor sol spinning solution, titanium oxide continuous fibers and nano fibers, and belongs to the technical field of functional fiber materials.
Background
Due to the rapid development of the industry, exhaust gas pollution, waste material pollution and waste water pollution have become serious problems facing the world. Water resources are an indispensable material basis for human life and economic development. At present, due to industrial wastewater and domestic wastewater, water pollution is increasingly serious, water resource shortage is aggravated, human survival is seriously influenced, and human development is restricted. Therefore, people are urgently required to find An effective method for treating sewage. Photocatalysis has attracted much attention since Fujishima and Honda reported that titanium oxide can be used to catalyze the photolysis of water. Photocatalysis is a process which utilizes light energy to degrade environmental pollutants and has the functions of bacteriostasis and sterilization, other substances are not needed in the process, the consumption of energy and materials can be effectively reduced, and the method is the cheapest and efficient method for treating sewage at present. In various photocatalytic materials (e.g. TiO) 2、CdS、WO3、Fe2O3、ZnO、ZnS、SnO2Etc.), titanium oxide has been widely used for environmental management due to its characteristics of higher photocatalytic activity, higher chemical stability, safety, non-toxicity, low cost, etc., and is a green catalyst. The basic principle of titanium oxide photocatalysis is based on the energy band theory of an N-type semiconductor, and when photons with energy larger than the forbidden band width (3.26ev) of titanium oxide are received, light-excited electrons transit to a conduction band to form conduction band electrons, and holes are left in a valence band. Due to the discontinuity of the semiconductor energy band, electrons and holes have long life time, and can move under the action of an electric field or in a diffusion mode to perform oxidation-reduction reaction with substances adsorbed on the surfaces of semiconductor catalyst particles, so that photocatalytic reaction is performed.
Titanium oxide has three crystal forms: anatase, rutile and brookite, wherein the first two crystal forms are common and have photocatalytic activity, but anatase is higher than rutile in photocatalytic activity because photoproduction electrons and holes formed in rutile are easier to recombine and cause photocatalytic reduction. Chinese patent document CN101314482A proposes a method for preparing anatase titanium oxide powder, which has relatively high photocatalytic activity, but has the problems of difficult recovery and easy generation of secondary pollution due to the limitation of powder form, and the photocatalytic activity is affected if the immobilization technique is adopted, which limits the popularization and application of titanium oxide powder.
The titanium oxide fiber is a polycrystalline ceramic fiber material, the diameter is hundreds of nanometers to tens of micrometers, the crystal grains are in a nanometer scale, the titanium oxide fiber is divided into short fibers and continuous fibers according to the length, the fibers with the length of millimeter level or centimeter level are generally called short fibers, and the fibers with the monofilament length of not less than 1 meter are called continuous fibers. Because the titanium oxide fiber has nano-scale crystal grains, proper crystal phase (anatase, rutile or both), extremely large specific surface area and higher adsorption capacity, the titanium oxide fiber has good photocatalytic activity, and the one-dimensional form of the fiber enables the titanium oxide fiber to be more easily recycled without loss to cause secondary pollution.
Since the 80's of the 20 th century, the preparation of titanium oxide fibers has been reported in a number of patents. Japanese patent documents JP55003371, JP55136126, JP55136127, JP5601792, JP60046927, JP60259625, JP1073030, JP1246139 and the like adopt a titanate dealkalization method to prepare titanium oxide fibers, and the fibers obtained by the method have a layered structure and high catalytic activity, but the fiber length is only micron-sized and can only be called fibrous titanium oxide, so the limitation on the length can not meet the requirement of the titanium oxide fibers. Japanese patent documents JP2019569 and JP4163317 and the like adopt an impregnation method to prepare titanium oxide fibers, and the method produces a precursor having an excessively high organic content and produces fibers having a low strength. US patent document US4166147 uses a sol-gel process for preparing titanium oxide fibers, which uses titanium alkoxide as a raw material to prepare a sol through hydrolysis and polycondensation reactions. The reaction process of the method is difficult to control, the sol is unstable, and the method is easy to gel and lose spinnability. There have been many patents reporting on the preparation of titania fibers from polytitanium precursors, but there are still many disadvantages. Chinese patent document CN1584156A proposes to use titanium tetrachloride as a titanium source, acetic acid or acetylacetone as a ligand, and select a suitable precipitation separation agent to prepare a sol that can be spun. The hydrolytic polycondensation process of the method is still difficult to control, and the impurity Cl is inevitably introduced by taking titanium tetrachloride as a titanium source -Affecting the quality of the subsequent sintering into titanium oxide fibers. CN100581648A prepares the titanium oxide fiber membrane through electrostatic spinning, and its spinning solution is to dissolve tetrabutyl titanate in absolute ethyl alcohol, and absolute ethyl alcohol plays a role in inhibiting hydrolysis, and the pH value of the solution is regulated and controlled by hydrochloric acid to control the hydrolysis polycondensation process of the solution, and this method has unstable control of the hydrolysis process, relatively complex preparation process, and poor sol spinnability and stability. Eyes of a user The preparation of the pre-titania fibers has two main problems: firstly, the price is high, the preparation process is complex, the sol stability is poor, and the high-quality titanium oxide fiber is difficult to prepare; secondly, impurities can be introduced in the preparation process, which affects the quality of the fiber. Therefore, on the premise of ensuring the fiber quality, a method with simple process and low cost is needed for preparing the titanium oxide fiber, so as to obtain the fiber with better strength, high titanium oxide solid content and good catalytic effect.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a polyacetylacetonato titanium precursor sol spinning solution, titanium oxide continuous fibers and nano fibers. The method comprises the steps of firstly synthesizing a titanium polyacetylacetonate precursor, preparing a sol spinning solution by using the titanium polyacetylacetonate precursor, respectively preparing titanium polyacetylacetonate precursor nano-fibers and continuous fibers by electrostatic spinning and dry spinning, and then preparing titanium oxide nano-fibers and continuous fibers by heat treatment. The preparation method has the advantages of simple process and low cost, can avoid the existence of impurity ions, and the prepared precursor sol has good spinnability, stability and difficult gelation, and the prepared fiber has high strength and good catalytic performance.
The technical scheme of the invention is as follows:
A preparation method of a polyacetylacetonato titanium precursor sol spinning solution comprises the following steps:
(1) Preparation of titanium polyacetylacetonate precursor
Weighing tetrabutyl titanate according to the molar ratio of tetrabutyl titanate to glacial acetic acid to water of (1-4) to (0.1-3.5), slowly adding the tetrabutyl titanate into glacial acetic acid, stirring and reacting for 2-4 h, adding water, stirring and reacting for 0.5-1 h to obtain a golden yellow solution, and concentrating the solution at 40-80 ℃ under reduced pressure to prepare solid powder; dissolving the obtained powder in an alcohol solvent according to the mass ratio of 1 to (1-4), adding acetylacetone and water according to the molar ratio of tetrabutyl titanate to acetylacetone to water of 1 to (0.6-1.4) to (0.1-2.5), stirring for reacting for 2-4 h, and concentrating under reduced pressure at the temperature of 40-80 ℃ to obtain a titanium polyacetylacetonate precursor;
The alcohol solvent is selected from one of absolute methanol and absolute ethanol or the combination thereof.
(2) Preparation of polyacetylacetonato titanium precursor sol spinning solution
Dissolving a titanium polyacetylacetonate precursor in an alcohol solvent according to the mass ratio of the titanium polyacetylacetonate precursor to the alcohol solvent of 100 (0.5-3) to 100-400, adding the auxiliary, and stirring and dissolving at the temperature of 10-60 ℃ to obtain a uniform and transparent titanium polyacetylacetonate precursor sol spinning solution;
The alcohol solvent is selected from one of absolute methanol and absolute ethanol or the combination thereof.
According to the invention, the molar ratio of tetrabutyl titanate, acetylacetone and water in the step (1) is preferably (0.6-1.4) to (0.5-1.5).
According to the invention, the mass ratio of the polyacetylacetonato titanium precursor to the alcohol solvent in the step (2) is preferably 100 (0.7-2) to (100-300);
Preferably, the auxiliary agent in step (2) is selected from one of polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, polyvinyl alcohol, polyacrylic acid, polyglycolic acid, polylactic acid, or a combination thereof.
A preparation method of titanium oxide nano-fiber comprises the following steps:
(i) Preparing a polyacetylacetonatitanium precursor sol spinning solution by adopting the preparation method of the polyacetylacetonatitanium precursor sol spinning solution;
(ii) Electrostatic spinning
placing the precursor sol spinning solution prepared in the step (i) into an injector with a stainless steel needle of a spinning device, feeding by using a micro-injection pump, and performing high-voltage electrostatic spinning to prepare precursor nano-fibers, wherein the electrostatic spinning conditions comprise that the environmental temperature is 20-35 ℃, the relative humidity is 20-70%, the applied voltage is 6-20 kV, the spinning feeding speed is 0.5-3.5 m L/h, and the distance between the needle and a rotary drum of a fiber collecting device is 8-35 cm;
(iii) Thermal treatment
(iii) heat treating the precursor nanofibers prepared in step (ii) in one of the following ways:
Heat treatment in air: placing the precursor nanofiber in a muffle furnace for heat treatment, heating to 400-1000 ℃ at a heating rate of 0.4-5 ℃/min under the air condition, preserving the heat for 1-3 hours to fully decompose and crystallize organic matters in the precursor fiber, and naturally cooling to room temperature to obtain solid titanium oxide nanofiber; alternatively, the first and second electrodes may be,
Heat treatment in steam: and (2) placing the precursor nanofiber in an atmosphere sintering furnace for heat treatment, heating to 100-200 ℃ at the heating rate of 3-5 ℃/min, introducing steam, heating to 300-900 ℃ at the heating rate of 0.5-3 ℃/min, stopping introducing the steam, preserving the heat for 1-3 h, and naturally cooling to room temperature to obtain the titanium oxide nanofiber.
According to the present invention, preferably, the stainless steel needle in step (ii) has model numbers of 4#, 5#, 6#, 7#, 8#, and 9#, and the inner diameters are 0.19, 0.26, 0.33, 0.41, 0.51, and 0.60mm, respectively; more preferably, the stainless steel needles are 5#, 6#, 7#, and 8 #.
according to the invention, the electrostatic spinning in the step (ii) is preferably carried out under the conditions that the ambient temperature is 20-30 ℃, the relative humidity is 30-50%, the applied voltage is 8-20 kV, the feeding speed is 1.0-3.0 m L/h, and the distance between a needle head and a rotary drum of a fiber collecting device is 10-30 cm.
According to the present invention, it is preferred that step (iii) is heat-treated in steam, said steam being water vapor;
Preferably, after the steam is introduced, the temperature is increased to 500-700 ℃ at a heating rate of 0.5-2 ℃/min.
According to the present invention, preferably, the atmosphere sintering furnace in step (iii) is a programmed sintering furnace, and the programmed sintering furnace is conventional equipment in the field; and carrying out medium-high temperature heat treatment.
A method for preparing titanium oxide continuous fibers comprises the following steps:
(a) Preparing a titanium polyacetylacetonate precursor sol spinning solution by adopting the preparation method of the titanium polyacetylacetonate precursor sol spinning solution, and then concentrating by a method of evaporating a solvent under reduced pressure to obtain a precursor sol spinning solution with the viscosity of 50-100 Pa.s (measured at 20 ℃), wherein the precursor sol spinning solution is used for dry spinning;
(b) Dry spinning
Placing the precursor sol spinning solution obtained in the step (a) into a spinning tank of a spinning device, performing vacuum defoamation for 5-20 min at the temperature of 20-45 ℃, applying the pressure of 0.5-2.0 MPa to the spinning solution in a steel cylinder nitrogen or metering pump mode under the conditions that the temperature is 10-45 ℃ and the relative humidity is 20-80% to extrude the spinning solution from a niobium-tantalum alloy spinneret plate with the aperture of 0.04-0.15 mm, and obtaining the titanium polyacetylacetonate precursor continuous fiber after drafting and collection;
(c) Pretreatment of
And (c) placing the precursor continuous fiber obtained in the step (b) into high-pressure steam equipment for pretreatment, wherein the pretreatment temperature is 100-160 ℃, the time is 10-120 min, and the pressure is 0.5-5 MPa.
Preferably, the pretreatment temperature is 120-145 ℃.
(d) Thermal treatment
And (c) placing the fiber pretreated in the step (c) into an atmosphere sintering furnace for heat treatment, heating to 100-200 ℃ at a heating rate of 3-6 ℃/min, introducing steam, heating to 400-1000 ℃ at a heating rate of 0.5-3 ℃/min, stopping introducing the steam, keeping the temperature for 1-3 h, and naturally cooling to room temperature to obtain the titanium oxide continuous fiber.
According to the invention, preferably, spinning is carried out in the step (b) under the conditions that the temperature is 20-40 ℃ and the relative humidity is 30-70%;
Preferably, the number of holes of the niobium-tantalum alloy spinneret plate is 50-500.
According to the present invention, it is preferred that the steam in step (d) is water vapor;
Preferably, the temperature is increased to 120-150 ℃ at the temperature rising rate of 5 ℃/min, steam is introduced, the temperature is increased to 600-800 ℃ at the temperature rising rate of 0.5-1.5 ℃/min, and the temperature is kept for 2h after the steam introduction is stopped.
The diameter of the titanium oxide continuous fiber prepared by the method is 20-100 mu m, the length of the titanium oxide continuous fiber is more than tens of meters, and the strength of the titanium oxide continuous fiber is 100 MPa-1.0 Gpa; the diameter of the obtained titanium oxide nano fiber is 400-1200 nm, the length of the obtained titanium oxide nano fiber is 2-6 cm, and the crystal form of the prepared titanium oxide fiber can be regulated and controlled to be anatase, rutile or both through different heat treatment processes.
The invention has the following beneficial effects:
(1) The invention adopts tetrabutyl titanate as a titanium source, can effectively avoid the introduction of other impurity ions, and the prepared polyacetylacetonatitanium sol spinning solution has the advantages of uniformity, good spinnability, high stability, no gel deterioration after being placed for more than 6 weeks, reusability of the spinning solution, re-dissolution in an alcohol solution after the alcohol solution in the sol volatilizes, still usability and stable performance.
(2) The invention uses acetylacetone as ligand, has simple synthesis process, easy operation, easy regulation and control of sol reaction process, no need of harsh reaction conditions and equipment in the reaction process, high production efficiency and low cost, and is beneficial to industrial production.
(3) The invention firstly prepares the precursor of the titanium polyacetylacetonate, and then adds the alcohol solvent, thus a small amount of the auxiliary agent can be added to obtain the spinning solution with good spinnability, and the adding quality of the auxiliary agent in the invention is far less than that of the titanium source.
(4) The invention adopts electrostatic spinning and dry spinning to respectively prepare precursor nano fiber and continuous fiber, and can prepare titanium oxide nano fiber and titanium oxide continuous fiber with the length of more than tens of meters by different heat treatment means, and the fiber has high strength and good quality.
(5) The titanium oxide fiber prepared by the invention is convenient to separate and collect, secondary pollution is avoided, the prepared titanium oxide crystal form can be regulated and controlled by different heat treatment processes, and the titanium oxide fiber serving as a photocatalyst has high photocatalytic activity.
Drawings
FIG. 1 shows IR spectra of poly (titanium acetylacetonate) precursor of example 1 of the present invention after heat treatment at different temperatures.
FIG. 2 is a thermogravimetric-differential thermal curve of a titanium polyacetylacetonate precursor in example 1 of the present invention.
FIG. 3 is a powder diffraction (XRD) pattern of the titanium polyacetylacetonate precursor of example 1 of the present invention after heat treatment at different temperatures.
FIG. 4 is a photograph of a titanium polyacetylacetonate precursor nanofiber obtained in example 2 of the present invention.
FIG. 5 is a photograph of the titanium oxide nanofibers obtained in example 2 of the present invention.
FIG. 6 is an SEM photograph of the titanium oxide nanofibers obtained in example 2 of the present invention, wherein the top right-hand insert is the diameter distribution of the titanium oxide nanofibers obtained.
FIG. 7 is an SEM photograph of the titanium oxide nanofibers obtained in example 2 of the present invention.
FIG. 8 is a photograph of a continuous fiber of titanium polyacetylacetonate precursor prepared by dry spinning in example 3 of the present invention.
FIG. 9 is a photograph of a continuous fiber of a titanium polyacetylacetonate precursor obtained in example 3 of the present invention.
FIG. 10 is a photograph of a titanium polyacetylacetonate precursor continuous fiber after high pressure steam pretreatment in example 3 of the present invention.
FIG. 11 is an SEM photograph of the titanium oxide continuous fiber obtained in example 3 of the present invention, wherein the upper right-hand insert is a diameter distribution chart of the titanium oxide continuous fiber obtained.
FIG. 12 is an SEM photograph of continuous titanium oxide fibers obtained in example 3 of the present invention.
FIG. 13 is an SEM photograph of continuous titanium oxide fibers obtained in example 3 of the present invention.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
The raw materials used in the examples are conventional raw materials, and the equipment used is conventional equipment, commercially available products.
Example 1
A preparation method of a polyacetylacetonato titanium precursor sol spinning solution comprises the following steps:
(1) Preparation of titanium polyacetylacetonate precursor
Weighing 100g of tetrabutyl titanate, 52.94g of glacial acetic acid and 5.29g of water according to the molar ratio of 1:3:1, fully stirring for reacting for 3 hours to obtain a golden yellow solution, placing the golden yellow solution in a flask, concentrating the golden yellow solution at 65 ℃ under reduced pressure for 6 hours until a dried solid product is obtained, and dissolving the golden yellow solution in 200g of anhydrous methanol; adding 29.41g of acetylacetone and 2.65g of water according to a molar ratio of tetrabutyl titanate to acetylacetone to water of 1:1:0.5, stirring for reaction for 3h to obtain a gold red solution, namely a titanium polyacetylacetonate solution, placing the gold red solution in a flask, and concentrating under reduced pressure at the temperature of 65 ℃ for 6h until a dry solid product, namely a titanium polyacetylacetonate precursor, is obtained.
And (3) testing the stability of the titanium polyacetylacetonate precursor: 10g of the titanium polyacetylacetonate precursor is dissolved in 20g of anhydrous methanol to form sol which can be continuously placed for more than 6 weeks and still be clear and transparent. Dissolving the precursor in anhydrous methanol, concentrating under reduced pressure to obtain powder, repeating for 5 times, dissolving in anhydrous methanol to obtain sol, and standing for more than 6 weeks to obtain clear transparent solution. Indicating that the stability of the precursor is good.
The precursor of titanium polyacetylacetonate is heat treated at 200 deg.C, 300 deg.C, 400 deg.C, 500 deg.C, 600 deg.C to obtain product with Infrared (IR) spectrum as shown in FIG. 1.
The polyacetylacetonato titanium precursor was subjected to differential thermal-thermogravimetric testing, and the results are shown in fig. 2.
The titanium polyacetylacetonate precursor was heat-treated at 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃ to obtain a product, which was subjected to an X-ray powder diffraction test, and the results are shown in fig. 3.
As can be seen from the IR spectrum of the titanium polyacetylacetonate precursor of FIG. 1, it is located at 1586cm -1And 1528cm -1Respectively, which are the C ═ O and C ═ C oscillations of the acetylacetone group, and the oscillation peak (1709 cm) corresponding to that of acetylacetone -1And 1622cm -1) The contrast is red-shifted, indicating that acetylacetone is in contrast to Ti 4+Coordination occurs. Located at 1600cm -1～900cm-1The absorption peak between the two belongs to acetylacetone group and is positioned at 812cm -1The peak at (A) is Ti-OH and is located at 662cm -1The peak of (a) is an outer ring plane vibration of the acetylacetone group C-H, and is located at 443cm -1The peak of (A) is Ti-O. With temperature As a result, acetylacetone was gradually decomposed. At 400 c, the organic matter is substantially decomposed and the absorption peak ascribed to Ti — O is largely changed, and when compared with the XRD spectrum of fig. 3, titanium oxide crystallization occurs. FIG. 2 is a thermogravimetric-differential thermal curve of a precursor, wherein it can be seen that the polyacetylacetonato titanium precursor mainly has 3 exothermic peaks respectively located at about 350 ℃, 500 ℃ and 760 ℃, and at 350 ℃, it can be seen from FIG. 3 that the exothermic peaks are caused by titanium oxide crystallization; at 500 ℃, according to thermogravimetric analysis, a larger weight loss exists at the moment, which is probably caused by carbon decomposition in the precursor; 760 ℃ it can be seen from FIG. 3 that the anatase to rutile phase transition occurred at this point, and therefore, it is likely that the exothermic peak was caused by the crystal phase transition.
(2) Preparation of polyacetylacetonato titanium precursor sol spinning solution
Dissolving 10g of titanium polyacetylacetonate precursor in 20g of anhydrous methanol at 30 ℃ and fully stirring to form a solution, adding 0.1g of polyethylene oxide (molecular weight of 100 ten thousand) into the solution, and continuously stirring and dissolving at 30 ℃ to obtain uniform and transparent sol spinning solution.
Example 2
A preparation method of titanium oxide nano-fiber comprises the following steps:
(i) Preparation of polyacetylacetonato titanium precursor sol spinning solution
Preparing a polyacetylacetonato titanium precursor sol spinning solution for electrostatic spinning by adopting the method in the embodiment 1;
(ii) Electrostatic spinning
and (3) placing the polyacetylacetonatitanium precursor sol spinning solution obtained in the step (i) into an injector with a stainless steel needle head of a spinning device, carrying out electrostatic spinning under the conditions that the temperature is 25 ℃, the relative humidity is 55%, the applied voltage value is 15kV, the stainless steel needle head type number 5#, the feeding speed of the injector is 2.5m L/h, and the distance between the stainless steel needle head and a rotary drum of a fiber collecting device is 20cm, and drawing and collecting the rotary drum to obtain the polyacetylacetonatitanium precursor fiber.
(iii) Thermal treatment
And (3) placing the polyacetylacetonato titanium precursor fiber obtained in the step (ii) into a muffle furnace for heat treatment, heating to 600 ℃ at the heating rate of 1 ℃/min under the air condition, preserving the temperature for 2 hours to ensure that organic matters in the precursor are fully decomposed and crystallized to be converted into titanium oxide nano-fibers, naturally cooling to room temperature, and keeping the obtained titanium oxide nano-fibers in an anatase phase with the diameter of 800-1200 nm, the length of 3-10 cm and high tensile strength.
Example 3
A method for preparing titanium oxide continuous fibers comprises the following steps:
(a) Preparing a titanium polyacetylacetonate precursor sol spinning solution by adopting the method in example 1, and then concentrating by a method of evaporating a solvent under reduced pressure to obtain a sol spinning solution with the viscosity of 75Pa & s (measured at 20 ℃) for dry spinning;
(b) Dry spinning
Placing the sol spinning solution prepared in the step (a) into a spinning tank of a spinning device, defoaming in vacuum for 10min at the temperature of 30 ℃, applying the pressure of 1.8MPa to the spinning solution in a steel cylinder nitrogen mode under the conditions that the temperature is 30 ℃ and the relative humidity is 40% to extrude the spinning solution in a niobium-tantalum alloy spinning plate with the thickness of 0.04mm, and obtaining the polyacetylacetonatitanium precursor continuous fiber after drafting and collecting;
(c) Pretreatment of
Putting the precursor continuous fiber obtained in the step (b) into high-pressure steam equipment for pretreatment, wherein the treatment temperature is 135 ℃, the treatment time is 20min, and the pressure is 2 MPa;
(d) Thermal treatment
And (c) placing the continuous fiber pretreated in the step (c) in an atmosphere sintering furnace for heat treatment, heating to 120 ℃ at the heating rate of 5 ℃/min, starting introducing water vapor, heating to 600 ℃ at the heating rate of 1 ℃/min, stopping introducing the water vapor, keeping the temperature for 2h, and naturally cooling to room temperature to obtain the titanium oxide continuous fiber.
Example 4
As described in example 2, except that in step (ii), the applied voltage was 20kV, the feeding speed of the syringe was 1.5m L/h, the diameter of the produced fiber was narrowed, and the yield was lowered.
Example 5
As described in example 2, except that in step (ii), the stainless steel needle type number was changed to 6#, the injector feed rate was 3.2m L/h, the diameter of the produced fiber was thickened, and the yield was improved.
Example 6
As described in example 2, except that in the step (ii), the take-up distance was adjusted to 15cm, the diameter of the prepared fiber was thickened.
Example 7
As described in example 2, except that in step (iii), the precursor fiber is placed in a muffle furnace for heat treatment, the temperature is raised to 500 ℃ at the heating rate of 1 ℃/min, the temperature is kept for 2h, and the titanium oxide nanofiber is obtained after natural cooling to room temperature. The prepared fiber has good appearance and strength, and the crystal form is anatase.
Example 8
As described in example 2, except that in step (iii), the precursor fiber is placed in a muffle furnace for heat treatment, the temperature is raised to 700 ℃ at a heating rate of 1 ℃/min, the temperature is kept for 2h, and the titanium oxide nanofiber is obtained after natural cooling to room temperature. The prepared fiber has good appearance and strength, and the crystal form is anatase.
Example 9
As described in example 2, except that in step (iii), the precursor fiber is placed in a muffle furnace for heat treatment, the temperature is raised to 800 ℃ at a heating rate of 1 ℃/min, the temperature is kept for 2h, and the titanium oxide nanofiber is obtained after natural cooling to room temperature. The prepared fiber has good appearance and strength, and the crystal form is anatase.
Example 10
As described in example 2, except that in step (iii), the precursor fiber is placed in a muffle furnace for heat treatment, the temperature is raised to 900 ℃ at a heating rate of 1 ℃/min, the temperature is kept for 2h, and the titanium oxide nanofiber is obtained after natural cooling to room temperature. The strength of the prepared fiber is reduced, and the crystal form is anatase.
Example 11
As described in example 2, except that the heat treatment in step (iii) was carried out in the following manner:
And (3) placing the precursor fiber in an atmosphere sintering furnace for heat treatment, heating to 120 ℃ at the heating rate of 5 ℃/min, introducing water vapor, heating to 600 ℃ at the heating rate of 1 ℃/min, stopping introducing the water vapor, keeping the temperature for 2h, and naturally cooling to room temperature to obtain the titanium oxide nanofiber. The prepared titanium oxide nano fiber is in a coexisting phase of anatase and rutile.
Example 12
The process is as described in example 2, except that in step (iii), the polyacetylacetonato titanium precursor fiber is placed in a muffle furnace for heat treatment, and the temperature is raised to 600 ℃ at a heating rate of 2 ℃/min under air conditions and is kept for 2 h. The prepared titanium oxide nano-fiber is anatase.
Example 13
As described in example 11, except that in step (iii), the temperature was first raised to 120 ℃ at a rate of 5 ℃/min, steam was introduced, and then the temperature was raised to 600 ℃ at a rate of 2 ℃/min. The prepared titanium oxide nano fiber is in a coexisting phase of anatase and rutile.
Example 14
As described in example 3, except that in the step (d), the temperature is raised to 120 ℃ at the temperature raising rate of 5 ℃/min, the introduction of the water vapor is started, the temperature is raised to 500 ℃ at the temperature raising rate of 1 ℃/min, the introduction of the water vapor is stopped, the temperature is kept for 2 hours, and the continuous titanium oxide fiber is obtained after natural cooling to the room temperature, wherein the crystalline phase of anatase and rutile coexist.
Example 15
As described in example 3, except that in the step (d), the temperature is raised to 120 ℃ at the temperature raising rate of 5 ℃/min, the water vapor is started to be introduced, then the temperature is raised to 700 ℃ at the temperature raising rate of 1 ℃/min, the water vapor is stopped to be introduced, the temperature is kept for 2h, and the continuous titanium oxide fiber is obtained after natural cooling to the room temperature, wherein the crystalline phase of anatase and rutile coexist.
Example 16
As described in example 3, except that in the step (d), the temperature is raised to 120 ℃ at the temperature raising rate of 5 ℃/min, the introduction of the water vapor is started, the temperature is raised to 800 ℃ at the temperature raising rate of 1 ℃/min, the introduction of the water vapor is stopped, the temperature is kept for 2 hours, and the continuous titanium oxide fiber is obtained after natural cooling to the room temperature, wherein the crystalline phase of anatase and rutile coexist.
Example 17
As described in example 3, except that in the step (d), the temperature is raised to 120 ℃ at the temperature raising rate of 5 ℃/min, the introduction of the water vapor is started, the temperature is raised to 900 ℃ at the temperature raising rate of 1 ℃/min, the introduction of the water vapor is stopped, the temperature is kept for 2 hours, and the continuous titanium oxide fiber is obtained after natural cooling to the room temperature, wherein the crystalline phase of anatase and rutile coexist.
Example 18
As described in example 3, except that in the step (d), the temperature is raised to 120 ℃ at the temperature raising rate of 5 ℃/min, the introduction of the water vapor is started, the temperature is raised to 1000 ℃ at the temperature raising rate of 1 ℃/min, the introduction of the water vapor is stopped, the temperature is kept for 2 hours, and the continuous titanium oxide fiber is obtained after natural cooling to the room temperature, wherein the crystalline phase of anatase and rutile coexist.
Example 19
As described in example 3, except that in step (d), the temperature is increased to 120 ℃ at a rate of 5 ℃/min, then the steam is introduced, the temperature is increased to 600 ℃ at a rate of 2 ℃/min, the steam is stopped to be introduced, then the temperature is maintained for 2h, and the titanium oxide continuous fiber is obtained after natural cooling to room temperature, wherein the crystalline phase of anatase and rutile coexist.
Comparative example 1
As described in example 1, except that 100g of tetrabutyl titanate, 15.00g of glacial acetic acid and 5.29g of water were weighed in a molar ratio of tetrabutyl titanate to glacial acetic acid to water of 1:0.85:1 in step (1), and reacted with stirring thoroughly for 3 hours to give a golden yellow solution, which was concentrated under reduced pressure at 65 ℃ to give no dry solid product.
Comparative example 2
As described in example 1, except that 100g of tetrabutyl titanate, 75.88g of glacial acetic acid and 5.29g of water were weighed in a molar ratio of tetrabutyl titanate to glacial acetic acid to water in step (1), and the reaction was stirred sufficiently for 3 hours, and a precipitate was precipitated in the obtained solution.
Comparative example 3
As described in example 1, except that 14.71g of acetylacetone was added in step (1) in a molar ratio of tetrabutyltitanate to acetylacetone to water of 1:0.5: 0.5.
And (3) precursor stability test: after the obtained titanium polyacetylacetonate precursor powder is placed for 5 weeks, the sol formed by dissolving the titanium polyacetylacetonate precursor powder in a methanol solvent gradually begins to form precipitates after being placed for 4 days.
Comparative example 4
As described in example 1, except that 44.13g of acetylacetone was added in step (1) in a molar ratio of tetrabutyltitanate to acetylacetone to water of 1:1.5:0.5, and the reaction was stirred for 3 hours to obtain a gold red solution, i.e., a titanium polyacetylacetonate solution. The gold red solution was placed in a flask and concentrated at 65 ℃ under reduced pressure for 10h, and a dry solid product was not easily obtained.
Comparative example 5
As described in example 1, except that 58.82g of acetylacetone was added in step (1) in a molar ratio of tetrabutyltitanate to acetylacetone to water of 1:2:0.5, and the reaction was stirred for 3 hours to obtain a deep red solution, i.e., a titanium polyacetylacetonate solution. The dark red solution was placed in a flask and concentrated at 65 ℃ under reduced pressure for 10h, and a dry solid product was not easily obtained.
Comparative example 6
The procedure is as described in example 1, except that acetylacetone alone and no water is added in step (1), and the reaction is stirred for 3 hours to obtain a dark red solution, i.e., a titanium polyacetylacetonate solution. The dark red solution was placed in a flask and concentrated at 65 ℃ under reduced pressure for 10h, and a dry solid product was not easily obtained.
Comparative example 7
the process is as described in example 2 except that the spinning feed rate in step (ii) is 4m L/h, resulting in a titanium polyacetylacetonate precursor fiber containing a large amount of beads, and the fiber prepared in step (iii) contains a large amount of shot with a coarser fiber diameter.
Comparative example 8
As described in example 3, except that the heat treatment process is direct sintering of the precursor fiber under air. The prepared fiber has poor strength and is easy to pulverize.
Claims (10)
1. A preparation method of a polyacetylacetonato titanium precursor sol spinning solution comprises the following steps:
(1) Preparation of titanium polyacetylacetonate precursor
Weighing tetrabutyl titanate according to the molar ratio of tetrabutyl titanate to glacial acetic acid to water of (1-4) to (0.1-3.5), slowly adding the tetrabutyl titanate into glacial acetic acid, stirring and reacting for 2-4 h, adding water, stirring and reacting for 0.5-1 h to obtain a golden yellow solution, and concentrating the solution at 40-80 ℃ under reduced pressure to prepare solid powder; dissolving the obtained powder in an alcohol solvent according to the mass ratio of 1 to (1-4), adding acetylacetone and water according to the molar ratio of tetrabutyl titanate to acetylacetone to water of 1 to (0.6-1.4) to (0.1-2.5), stirring for reacting for 2-4 h, and concentrating under reduced pressure at the temperature of 40-80 ℃ to obtain a titanium polyacetylacetonate precursor;
The alcohol solvent is selected from one of absolute methanol and absolute ethanol or the combination thereof;
(2) Preparation of polyacetylacetonato titanium precursor sol spinning solution
Dissolving a titanium polyacetylacetonate precursor in an alcohol solvent according to the mass ratio of the titanium polyacetylacetonate precursor to the alcohol solvent of 100 (0.5-3) to 100-400, adding the auxiliary, and stirring and dissolving at the temperature of 10-60 ℃ to obtain a uniform and transparent titanium polyacetylacetonate precursor sol spinning solution;
The alcohol solvent is selected from one of absolute methanol and absolute ethanol or the combination thereof.
2. The method for preparing a titanium polyacetylacetonate precursor sol spinning solution according to claim 1, wherein the molar ratio of tetrabutyl titanate, acetylacetone and water in the step (1) is 1 (0.6-1.4) to (0.5-1.5).
3. The method for preparing the titanium polyacetylacetonate precursor sol spinning solution according to claim 1, wherein the titanium polyacetylacetonate precursor in the step (2) is prepared by mixing 100 (0.7-2) parts by mass of an auxiliary agent, namely an alcohol solvent and 100-300 parts by mass of an auxiliary agent;
The auxiliary agent is selected from one or the combination of polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, polyvinyl alcohol, polyacrylic acid, polyglycolic acid and polylactic acid.
4. A preparation method of titanium oxide nano-fiber comprises the following steps:
(i) Preparing a titanium polyacetylacetonate precursor sol spinning solution by using the method for preparing the titanium polyacetylacetonate precursor sol spinning solution according to any one of claims 1 to 3;
(ii) Electrostatic spinning
placing the polyacetylacetonato titanium precursor sol spinning solution prepared in the step (i) into an injector with a stainless steel needle of a spinning device, feeding by using a micro-injection pump, and performing high-voltage electrostatic spinning to obtain precursor nano-fibers, wherein the electrostatic spinning conditions comprise that the environmental temperature is 20-35 ℃, the relative humidity is 20-70%, the applied voltage is 6-20 kV, the spinning feeding speed is 0.5-3.5 m L/h, and the distance between the needle and a rotary drum of a fiber collecting device is 8-35 cm;
(iii) Thermal treatment
(iii) heat treating the precursor nanofibers prepared in step (ii) in one of the following ways:
Heat treatment in air: placing the precursor nanofiber in a muffle furnace for heat treatment, heating to 400-1000 ℃ at a heating rate of 0.4-5 ℃/min under the air condition, preserving the heat for 1-3 hours to fully decompose and crystallize organic matters in the precursor fiber, and naturally cooling to room temperature to obtain solid titanium oxide nanofiber; alternatively, the first and second electrodes may be,
Heat treatment in steam: and (2) placing the precursor nanofiber in an atmosphere sintering furnace for heat treatment, heating to 100-200 ℃ at the heating rate of 3-5 ℃/min, introducing steam, heating to 300-900 ℃ at the heating rate of 0.5-3 ℃/min, stopping introducing the steam, preserving the heat for 1-3 h, and naturally cooling to room temperature to obtain the titanium oxide nanofiber.
5. The method for preparing titanium oxide nanofibers according to claim 4, wherein the stainless steel tips in step (ii) are 4#, 5#, 6#, 7#, 8#, and 9#, and have inner diameters of 0.19, 0.26, 0.33, 0.41, 0.51, and 0.60mm, respectively.
6. the method for preparing titanium oxide nanofibers according to claim 4, wherein the conditions for electrospinning in step (ii) are that the ambient temperature is 20-30 ℃, the relative humidity is 30-50%, the applied voltage is 8-20 kV, the feeding speed is 1.0-3.0 m L/h, and the distance between the needle and the drum of the fiber collecting device is 10-30 cm.
7. The method for preparing titanium oxide nanofibers according to claim 4, wherein step (iii) is heat-treated in steam, said steam being water vapor; after the steam is introduced, the temperature is increased to 500-700 ℃ at the heating rate of 0.5-2 ℃/min.
8. A method for preparing titanium oxide continuous fibers comprises the following steps:
(a) Preparing a titanium polyacetylacetonate precursor sol spinning solution by adopting the preparation method of the titanium polyacetylacetonate precursor sol spinning solution according to any one of claims 1 to 3, and then concentrating by a method of evaporating a solvent under reduced pressure to obtain a precursor sol spinning solution with the viscosity of 50-100 Pa.s (measured at 20 ℃) for dry spinning;
(b) Dry spinning
Placing the precursor sol spinning solution obtained in the step (a) into a spinning tank of a spinning device, performing vacuum defoamation for 5-20 min at the temperature of 20-45 ℃, applying the pressure of 0.5-2.0 MPa to the spinning solution in a steel cylinder nitrogen or metering pump mode under the conditions that the temperature is 10-45 ℃ and the relative humidity is 20-80% to extrude the spinning solution from a niobium-tantalum alloy spinneret plate with the aperture of 0.04-0.15 mm, and obtaining the titanium polyacetylacetonate precursor continuous fiber after drafting and collection;
(c) Pretreatment of
Putting the precursor continuous fiber obtained in the step (b) into high-pressure steam equipment for pretreatment, wherein the pretreatment temperature is 100-160 ℃, the time is 10-120 min, and the pressure is 0.5-5 Mpa;
(d) Thermal treatment
And (c) placing the fiber pretreated in the step (c) into an atmosphere sintering furnace for heat treatment, heating to 100-200 ℃ at a heating rate of 3-6 ℃/min, introducing steam, heating to 400-1000 ℃ at a heating rate of 0.5-3 ℃/min, stopping introducing the steam, keeping the temperature for 1-3 h, and naturally cooling to room temperature to obtain the titanium oxide continuous fiber.
9. The method for preparing titanium oxide continuous fibers according to claim 8, wherein the spinning is performed in the step (b) at a temperature of 20 to 40 ℃ and a relative humidity of 30 to 70%; the number of holes of the niobium-tantalum alloy spinneret plate is 50-500.
10. The method of preparing titanium oxide continuous fibers according to claim 8, wherein the steam in the step (d) is water vapor; heating to 120-150 ℃ at a heating rate of 5 ℃/min, introducing steam, heating to 600-800 ℃ at a heating rate of 0.5-1.5 ℃/min, stopping introducing steam, and then preserving heat for 2 hours.
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