CN108411489A - The preparation method of PET/ porous carbon hybrid materials - Google Patents
The preparation method of PET/ porous carbon hybrid materials Download PDFInfo
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- CN108411489A CN108411489A CN201810308577.7A CN201810308577A CN108411489A CN 108411489 A CN108411489 A CN 108411489A CN 201810308577 A CN201810308577 A CN 201810308577A CN 108411489 A CN108411489 A CN 108411489A
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/435—Polyesters
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- 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
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
Abstract
The invention discloses a kind of preparation methods of PET/ porous carbons hybrid material, carry out according to the following steps successively：First step is to prepare monkey grass based active carbon fiber as porous carbon；Second step is to prepare PET/ porous carbon spinning solutions, and third step is that PET/ porous carbon hybridized fiber films are made in PET spinning solutions using electrostatic spinning machine；Four steps is performed etching to PET/ porous carbon hybridized fiber films using lye.The present invention considers influence of the addition of porous carbon to performances such as mechanical property, specific surface area and porositys, can prepare best PET/ porous carbon hybrid materials for each individual event performance requirement.PET/ porous carbon hybrid materials prepared by the present invention, the specific surface area of tunica fibrosa is larger, and filtering and adsorption capacity are relatively strong, and durability is good.
Description
Technical field
The present invention relates to Static Spinning technical fields.
Background technology
Electrostatic spinning technique comes across in the 1940s, American A.Formhals first proposes the big of electrostatic spinning
Concept is caused, and has applied for patent.To the end of the seventies in last century, Taylor drops in high-voltage electricity according to the spinning solution at spinning syringe needle
Variation under field action, it is indicated that the mutual relationship change situation of the surface tension of electric field force and spinning solution, electric field force are slow
It is slow to increase to when reaching the state relatively balanced with specific surface tension, by the liquid that is squeezed out in the syringe needle of nozzle from ball
Shape gradually become tapered form, the number of degrees of cone angle are 49.3 ° at this time, i.e., referred to as Taylor cone.
When electric field force is gradually increased to the surface tension more than spinning solution, spinning solution is elongated and from Taylor
The top of cone ejects, and is finally received in receiving roll and forms fiber.
The Baum garten of DuPont Corporation are prepared for out when 1971 by using electrostatic spinning process
The polyacrylonitrile of submicron order (PAN) fiber；1981, the Donaldson companies in the U.S. prepared Ultraweb nanometers
Fibrous filter material opens electrostatic spinning fiber and is widely applied foreground in filtering industry.
From the 1990s, more and more extensive with the application of nano-fiber material, the art is to Nanowire
More stringent requirements are proposed for the moulding process of dimension, while also providing the development space of new bigger, to prepare various Nanowires
Dimension creates better condition.
In the narrow sense, the production technologies such as nanofiber more traditional spinning process such as melt spinning, solution-polymerized SBR
It hardly results in, because the above method spins fibre diameter obtained about between 5 ~ 500 μm.
People set about a series of experiment to electrostatic spinning process and further investigate, research the result shows that utilize
The fineness that the fineness for the nanofiber that the method for electrostatic spinning manufactures spins out the fiber come relative to traditional technique is wanted
Apparent much smaller, diameter, which is substantially all, has reached nanoscale.
Electrostatic spinning principle
The cardinal principle of method of electrostatic spinning is by applying a certain amount of high electricity at syringe needle or directly to macromolecule spinning solution
Pressure, on the surface of the drop at syringe needle, due to the Relatively centralized of charge, mutually exclusive to produce between charge shows
As the droplet ejected from syringe needle gradually forms the shape of circular cone.The power of repulsion between charge is also gradually increasing
Become larger by force, when the repulsive force increase of charge to a certain extent when（When the surface tension of i.e. remote super spinning solution）, spinning liquid
Front end from syringe needle ejects straight.Because the solution thread sprayed is tapered, the charge on surface it is close
Degree gradually becomes larger, and the repulsive force of charge becomes very strong, to carry out the stretching of deeper to solution stream.Just at this moment, molten
The volatilization that the surface area of liquid stream is carried out due to increased very swift and violent and solvent, thus forms our institutes in receiving roll
Nanofiber obtained.
Electrostatic spinning apparatus
Electrostatic spinning machine is mainly by high voltage power supply, syringe, extruder, the nozzle for connecting syringe（Syringe needle can）, connect
Receive roller and computer connecting device.The solution of the polymer of required spinning is infused in syringe.In the preceding termination gold of syringe needle
Belong to electrode to be connected with high voltage power supply as anode.The device of the reception of the earth is connected as cathode.
Invention content
The purpose of the present invention is to provide a kind of filtering and the systems of the stronger PET/ porous carbons hybrid material of adsorption capacity
Preparation Method.
To achieve the above object, the preparation method of PET/ porous carbon hybrid materials of the invention successively according to the following steps into
Row：
First step is to prepare monkey grass based active carbon fiber as porous carbon；
Second step is to prepare PET/ porous carbon spinning solutions, and the component and parts by weight of PET/ porous carbon spinning solutions are：16
Part PET, 0.5 to 2.5 part of porous carbon and 81.5 to 83.5 parts of trifluoroacetic acids and mixed solvent made of dichloromethane；
Third step is that PET/ porous carbon hybridized fiber films are made in PET spinning solutions using electrostatic spinning machine；
Four steps is performed etching to PET/ porous carbon hybridized fiber films using lye, and it is miscellaneous in PET/ porous carbons to increase porous carbon
Chemical fibre ties up the exposed amount on membrane fiber surface, obtains PET/ porous carbon hybrid materials.
The specific method that the second step prepares spinning solution includes following sub-step：
（1）PET slices is 15-17 hours dry in vacuum drying chamber, and 170 ± 1 DEG C of drying temperature is put into drying after dry
It is for use in device；
（2）By trifluoroacetic acid and dichloromethane according to volume ratio 1：1 makes mixed solvent；It is positioned over the iodine flask of dried and clean
In；Calculating weighs（1）The obtained PET of sub-step is simultaneously added in the mixed solvent, then calculates and weighs porous carbon to mixing
In solvent, PET/ porous carbon spinning solutions are made；
（3）The rotor of magnetic stirring apparatus is put into after being stirred 4 hours in iodine flask to form uniform spinning solution for use.
The first step includes following sub-step：
（1）Pre-oxidation；The monkey grass for being derived from palm living is cut into 3 ± 0.1 centimetres of monkey grass section, by monkey grass
Section washs and dries to be placed in Muffle furnace and pre-oxidized, and Pre oxidation is 250 DEG C, and preoxidation time is 3 ± 0.1 hours；
（2）Activation；By the monkey grass after pre-oxidation and the zinc chloride in mass ratio 1 as change agent living：1 is mixed；
（3）It is soaked in water 24 ± 0.1 hours to the mixture of monkey grass and zinc chloride, monkey grass is made to be mixed with zinc chloride
It is even；Then the mixture of monkey grass and zinc chloride is positioned over ventilation to dry 2 ± 0.1 hours, then by monkey grass and chlorine
The mixture for changing zinc is placed on heat drying 2 hours in baking oven, and baking oven heating temperature is 120 ± 3 DEG C；It, will be brown after heat drying
The mixture of palmitic acid fiber and zinc chloride takes out；
（4）The mixture of monkey grass and zinc chloride is carbonized using tube type resistance furnace；Specifically by monkey grass and chlorine
After the mixture of change zinc is put into tube type resistance furnace, the temperature in tube type resistance furnace is risen to 800 DEG C, after then being kept for 3 hours again
Gradually cooling, waits for that temperature is cooled to room temperature, and takes out the mixture of monkey grass and zinc chloride；
（5）Use quality Baidu that the mixture of monkey grass and zinc chloride is impregnated and rinsed than the hydrochloric acid for 20%, until
Basic anhydride in the mixture of monkey grass and zinc chloride are neutralized to by hydrochloric acid be in neutrality after, filtered, dried successively
With weigh, obtain monkey grass based active carbon fiber.
The concrete operations of the third step are：
The PET/ porous carbon spinning solutions prepared in second step are drawn using syringe, and syringe is mounted on electrostatic spinning machine
On, make the piston of syringe and promote that pump is connected and the outlet of syringe is connected by hose with the nozzle of electrostatic spinning machine,
The distance between the receiving roll of the nozzle of electrostatic spinning machine and electrostatic spinning machine is adjusted to 16 centimetres；
By masking foil it is smooth in receiving roll be used for receive fiber；The spinning voltage of electrostatic spinning machine is set as 25,000
Volt；It it is 100 revs/min by the rotational speed regulation of the receiving roll of electrostatic spinning machine；Start and pump is promoted to promote syringe, keeps PET/ porous
Carbon spinning solution is sprayed onto by nozzle on the masking foil in receiving roll, and with the rotation of receiving roll, it is big that thickness is formed in receiving roll
In the PET/ porous carbon hybridized fiber films equal to 150 microns；The formation time of PET/ porous carbon hybridized fiber films is 3.5 ± 0.3
Hour.
The concrete operations of the four steps are：
The sodium hydroxide solution that mass percent is 5% is first prepared, then PET/ porous carbon hydridization made of clip third step
Tunica fibrosa places it in and carries out immersion etching in sodium hydroxide solution, and it is 5 ± 0.2 minutes to impregnate etch period, after impregnating etching
It dries, finally by the PET/ porous carbon hybridized fiber films after alkaline etching in valve bag.
In second step, the parts by weight of PET, porous carbon and mixed solvent are following five in PET/ porous carbon spinning solutions
Any group in group parts by weight：
（1）16 parts of PET, 0.5 part of porous carbon, 83.5 parts of trifluoroacetic acids and mixed solvent made of dichloromethane；
（2）16 parts of PET, 1.0 parts of porous carbons, 83 parts of trifluoroacetic acids and mixed solvent made of dichloromethane；
（3）16 parts of PET, 1.5 parts of porous carbons, 82.5 parts of trifluoroacetic acids and mixed solvent made of dichloromethane；
（4）16 parts of PET, 2.0 parts of porous carbons, 82 parts of trifluoroacetic acids and mixed solvent made of dichloromethane；
（5）16 parts of PET, 2.5 parts of porous carbons, 81.5 parts of trifluoroacetic acids and mixed solvent made of dichloromethane.
The present invention has the advantage that：
The present invention considers influence of the addition of porous carbon to performances such as mechanical property, specific surface area and porositys, can be directed to
Each individual event performance requirement prepares best PET/ porous carbon hybrid materials.
The palmityl porous carbon materials that the present invention researches and develops and PET solution blendings, PET/ porous carbons are prepared by Static Spinning
Then hybrid material further performs etching its hybrid material, make its porous carbon materials partial denudation in fiber surface, improve
Its specific surface area.
PET/ porous carbon hybrid materials prepared by the present invention, the specific surface area of tunica fibrosa is larger, filtering and adsorption energy
Power is relatively strong, and durability is good.
It was found that, when preparing PET/ porous carbon spinning solutions, in the mixed solvent PET, porous carbon and mixed solvent
Parts by weight are 16：1.5：When 82.5 and 16：2.0：When 82, the strainability of obtained PET/ porous carbon hybrid materials and
Absorption property is best, but its mechanism has no theoretical direction.Scanning electron microscopic observation and progress specific surface area after many experiments
After analysis, find, when the parts by weight of porous carbon are 1.5, doughnut occur in tunica fibrosa, thus it is more to enhance PET/
The filtering of hole carbon hybrid material and adsorption capacity.The mechanism occurred as doughnut under these conditions needs further
It explores.Inventor has found simultaneously, although theoretically the number of porous carbon is more, then specific surface area can be bigger, and many experiments are equal
When showing that the parts by weight of porous carbon are 2.0, PET/ porous carbon hybrid materials（Tunica fibrosa）Specific surface area it is maximum；It is this existing
As the reason of also up for further exploring.Although needing also exist for further exploring place in theory, this is not interfered
Applicant therefrom finds out the understanding of regularity：
Using（3）Group and the（4）Group（That is embodiment three and example IV）Mixed solvent is made in weight proportion, obtains having most
The PET/ porous carbon hybrid materials of good filtering and adsorption capacity；
Using（5）Group weight proportion mixed solvent is made, can prepare with best mechanical property and tunica fibrosa it is the most equal
Even PET/ porous carbon hybrid materials, and the conductivity of the solution in second step is maximum.
Using（1）Mixed solvent is made in group weight proportion, and the conductivity of the solution in the second step of preparation process is most
It is small.
The result of study of inventor, which shows that monkey grass based active carbon fiber is wrapped in tunica fibrosa, greatly to be increased
The mechanical property of strong tunica fibrosa.If monkey grass based active carbon fiber dosage is excessive, specific surface area can reduce, and cause to filter
Performance and absorption property are deteriorated；The yield rate of Static Spinning decreases simultaneously, therefore considers, and it is more that second step prepares PET/
When the carbon spinning solution of hole, the parts by weight of monkey grass based active carbon fiber are no more than 2.5.
It is required according to the difference to PET/ porous carbon hybrid material performances, it can be with when preparing PET/ porous carbon spinning solutions
Take different proportionings.
Using the monkey grass based active carbon fiber prepared by the present invention as porous carbon, PET/ porous carbons are substantially increased
Success rate prepared by hybrid material.Wherein, 20% hydrochloric acid is not being used to impregnate the mixture of monkey grass and zinc chloride
When with rinsing, the monkey grass based active carbon fiber for preparing as porous carbon so that the PET/ porous carbons that prepare it is miscellaneous
The defect rate for changing material is excessively high.Through research just discovery this is because zinc chloride as activator, although activation effect is good,
For will produce basic anhydride after monkey grass and remain in monkey grass.There is this to recognize, the invention talent obtains
The technical solution of removal basic anhydride.
Description of the drawings
Fig. 1 is the variation relation curve graph of different porous concentration of carbons and electrical conductivity of solution；
Fig. 2 is the curve graph of spinning solution viscosity and shear stress under different porous carbon contents；
Fig. 3 is the graph of relation of porous carbon content and the specific surface area of PET/ porous carbon hybridized fiber films；
Fig. 4 is the scanning electron microscope (SEM) photograph of the PET/ porous carbon hybridized fiber films before and after alkaline etching in embodiment one；
Fig. 5 is the scanning electron microscope (SEM) photograph of the PET/ porous carbon hybridized fiber films before and after alkaline etching in embodiment two；
Fig. 6 is the scanning electron microscope (SEM) photograph of the PET/ porous carbon hybridized fiber films before and after alkaline etching in embodiment three；
Fig. 7 is the scanning electron microscope (SEM) photograph of the PET/ porous carbon hybridized fiber films before and after alkaline etching in example IV；
Fig. 8 is the scanning electron microscope (SEM) photograph of the PET/ porous carbon hybridized fiber films before and after alkaline etching in embodiment five.
Specific implementation mode
The present invention provides a kind of preparation methods of PET/ porous carbons hybrid material, carry out according to the following steps successively：
First step is to prepare monkey grass based active carbon fiber as porous carbon；
Second step is to prepare PET/ porous carbon spinning solutions, and the component and parts by weight of PET/ porous carbon spinning solutions are：16
Part PET, 0.5 to 2.5 part（Including endpoints thereof）Porous carbon and 81.5 to 83.5 parts of trifluoroacetic acids are mixed with made of dichloromethane
Bonding solvent；The conductivity and viscosity of each group solution are tested.
Third step is that PET/ porous carbon hybridized fiber films are made in PET spinning solutions using electrostatic spinning machine；And to fibre
Specific surface area, porosity, mechanical property and the pattern etc. of dimension film are tested.
Four steps is performed etching to PET/ porous carbon hybridized fiber films using lye, and it is porous in PET/ to increase porous carbon
The exposed amount on carbon hybridized fiber membrane fiber surface, obtains PET/ porous carbon hybrid materials.
The specific method that the second step prepares spinning solution includes following sub-step：
（1）By PET（That is polyester）Slice is 15-17 hours dry in vacuum drying chamber（It is preferred that 16 hours）, drying temperature 170
It ± 1 DEG C, is put into drier after dry for use；
（2）By trifluoroacetic acid（CF3COOH）And dichloromethane（CH2Cl2）According to volume ratio 1：1 makes 15 milliliters of mixed solvents；
It is positioned in 100 milliliters of iodine flasks of dried and clean；Calculating weighs（1）The obtained PET of sub-step and be added to mixing it is molten
In agent, then calculates and weigh porous carbon in the mixed solvent, PET/ porous carbon spinning solutions are made；
Calculating the result weighed ensures that the parts by weight of PET, porous carbon and mixed solvent in PET/ porous carbon spinning solutions are：16
Part PET,（0.5-2.5）：（81.5-83.5）.
（3）The rotor of magnetic stirring apparatus is put into after being stirred 4 hours in iodine flask to form uniform spinning solution for use.
The first step includes following sub-step：
（1）Pre-oxidation；The monkey grass for being derived from palm living is cut into 3 ± 0.1 centimetres of monkey grass section, by monkey grass
Section washs and dries to be placed in Muffle furnace and pre-oxidized, and Pre oxidation is 250 DEG C, and preoxidation time is 3 ± 0.1 hours；
（2）Activation；By the monkey grass after pre-oxidation and the zinc chloride as change agent living（ZnCl2）In mass ratio 1：1 is mixed
It closes；
（3）It is soaked in water 24 ± 0.1 hours to the mixture of monkey grass and zinc chloride, monkey grass is made to be mixed with zinc chloride
It is even；Then the mixture of monkey grass and zinc chloride is positioned over ventilation to dry 2 ± 0.1 hours, then by monkey grass and chlorine
The mixture for changing zinc is placed on heat drying 2 hours in baking oven, and baking oven heating temperature is 120 ± 3 DEG C；It, will be brown after heat drying
The mixture of palmitic acid fiber and zinc chloride takes out and uses electronic balance weighing；
（4）The mixture of monkey grass and zinc chloride is carbonized using tube type resistance furnace；Specifically by monkey grass and chlorine
After the mixture of change zinc is put into tube type resistance furnace, the temperature in tube type resistance furnace is risen to 800 DEG C, after then being kept for 3 hours again
Gradually cooling, waits for that temperature is cooled to room temperature, and takes out the mixture of monkey grass and zinc chloride and uses electronic balance weighing；
（5）Use quality Baidu that the mixture of monkey grass and zinc chloride is impregnated and rinsed than the hydrochloric acid for 20%, until
Basic anhydride in the mixture of monkey grass and zinc chloride are neutralized to by hydrochloric acid be in neutrality after, filtered, dried successively
With weigh, obtain monkey grass based active carbon fiber.
Using the monkey grass based active carbon fiber prepared by the present invention as porous carbon, PET/ porous carbons are substantially increased
Success rate prepared by hybrid material.Wherein, 20% hydrochloric acid is not being used to impregnate the mixture of monkey grass and zinc chloride
When with rinsing, the monkey grass based active carbon fiber for preparing as porous carbon so that the PET/ porous carbons that prepare it is miscellaneous
The defect rate for changing material is excessively high.Through research just discovery this is because zinc chloride as activator, although activation effect is good,
For will produce basic anhydride after monkey grass and remain in monkey grass.There is this to recognize, the invention talent obtains
The technical solution of removal basic anhydride.
The mixture of monkey grass and zinc chloride is impregnated and washed using acid too strong acid solution, it can be in certain journey
The performance of porous carbon is damaged on degree；Acid too small, then N-process is too long.20% hydrochloric acid is then ensureing the same of porous carbon performance
When realize neutralize speed maximize.
The concrete operations of the third step are：
The PET/ porous carbon spinning solutions prepared in second step are drawn using syringe, and syringe is mounted on electrostatic spinning machine
On, make the piston of syringe and promote that pump is connected and the outlet of syringe is connected by hose with the nozzle of electrostatic spinning machine,
The distance between the receiving roll of the nozzle of electrostatic spinning machine and electrostatic spinning machine is adjusted to 16 centimetres；
By masking foil it is smooth in receiving roll be used for receive fiber；The spinning voltage of electrostatic spinning machine is set as 25,000
Volt；It it is 100 revs/min by the rotational speed regulation of the receiving roll of electrostatic spinning machine；Start and pump is promoted to promote syringe, keeps PET/ porous
Carbon spinning solution is sprayed onto by nozzle on the masking foil in receiving roll, and with the rotation of receiving roll, it is big that thickness is formed in receiving roll
In the PET/ porous carbon hybridized fiber films equal to 150 microns；The formation time of PET/ porous carbon hybridized fiber films is 3.5 ± 0.3
Hour.
The concrete operations of the four steps are：
First prepare the sodium hydroxide that mass percent is 5%（NaOH）Solution, then PET/ made of clip third step is porous
Carbon hybridized fiber film places it in and carries out immersion etching in sodium hydroxide solution, and it is 5 ± 0.2 minutes to impregnate etch period, is impregnated
It is dried after etching, finally by the PET/ porous carbon hybridized fiber films after alkaline etching in valve bag.
Embodiment one
In second step, the parts by weight of PET, porous carbon and mixed solvent are in PET/ porous carbon spinning solutions：
（1）16 parts of PET, 0.5 part of porous carbon, 83.5 parts of trifluoroacetic acids and mixed solvent made of dichloromethane.
Embodiment two
In second step, the parts by weight of PET, porous carbon and mixed solvent are in PET/ porous carbon spinning solutions：
（2）16 parts of PET, 1.0 parts of porous carbons, 83 parts of trifluoroacetic acids and mixed solvent made of dichloromethane.
Embodiment three
In second step, the parts by weight of PET, porous carbon and mixed solvent are in PET/ porous carbon spinning solutions：
（3）16 parts of PET, 1.5 parts of porous carbons, 82.5 parts of trifluoroacetic acids and mixed solvent made of dichloromethane.
Example IV
In second step, the parts by weight of PET, porous carbon and mixed solvent are in PET/ porous carbon spinning solutions：
（4）16 parts of PET, 2.0 parts of porous carbons, 82 parts of trifluoroacetic acids and mixed solvent made of dichloromethane.
Embodiment five
In second step, the parts by weight of PET, porous carbon and mixed solvent are in PET/ porous carbon spinning solutions：
（5）16 parts of PET, 2.5 parts of porous carbons, 81.5 parts of trifluoroacetic acids and mixed solvent made of dichloromethane.
Performance measurement
One, the conductivity of the PET/ porous carbon spinning solutions in the second step of five embodiments is measured respectively.
It is right using its using the DDS-307A type electric conductivity instrument that Shanghai INESA Scientific Instrument Co., Ltd. produces
The conductivity of PET/ porous carbon spinning solutions is measured.Its determination step is：It is first turned on power supply, by one pole of temperature sense
It is inserted into distilled water, and hot water is added and adjusts water temperature to 30 DEG C；DJS-1C type platinum black electrodes are cleaned up, with filter paper water
Divide wiped clean, then is dried up with ear washing bulb.PET/ porous carbon spinning solution conductivity is tested, it is (molten which is inserted into prepare liquid
Liquid will not have electrode slice), reading when numerical stability is the conductivity of prepare liquid.It has to keep temperature during test
It is 30 DEG C to spend constant.
Measurement result is as shown in Figure 1.Generally, increase with the increase of porous carbon content when the conductivity of spinning solution.
Two, the viscosity of the PET/ porous carbon spinning solutions in the second step of five embodiments is measured respectively.
Viscosity apparatus is rotated automatically using II+PRO types of RVDV-, and the PET/ porous carbons measured in each embodiment second step are spun
The zero-shear viscosity of silk solution.Substantially operating procedure is for it：The viscosity apparatus program switch on computer and computer is opened, then opens viscosity
Instrument adjusts the pattern on instrument control panel to " External Mode "；The Rheocalc softwares of computer are opened, instrument is adjusted
The use of port is PORT COM " 1 ", removes the rotor unloaded on instrument, opens display board and carry out school zero；After the completion of calibration, remove
Liquid filling tube pours into solution, then liquid filling tube is loaded onto；Rotor is then loaded onto, the rich quasi- polyester liquid program of power Darts is loaded and is surveyed
Examination, rotor start to rotate, can show multi-group data on computer when rotor stops operating, reach a concentration of solution when equilibrium valve
Zero-shear viscosity.The viscosity of the PET/ porous carbon spinning solutions in five embodiment second steps is divided through the above steps
It does not measure, the results are shown in Figure 2.
When porous carbon content is relatively low, viscosity is as the variation of shear stress is not it is obvious that working as the content ratio of porous carbon
When higher, viscosity starts significantly with the variation of shear stress.Spinning solution can be found out according to fig. 2 under each porous carbon content
Viscosity.
Table 1 is the viscosity gauge of PET/ porous carbons spinning solution made of different content porous carbon.
| Porous carbon content/% | 0.5 | 1.0 | 1.5 | 2.0 | 2.5 |
| Viscosity/cP | 64 | 92 | 158 | 216 | 232 |
On the whole, with the increase of porous carbon content, the viscosity of spinning solution gradually increases.But when the porous carbon being added
Amount when be not very much, the variation amplification of viscosity is not very big；And when porous carbon content increases to 2.0% or more,
The viscosity of spinning solution increases very big.
Three, PET/ porous carbons hybrid material（PET/ porous carbon hybridized fiber films）Mechanics performance determining
Mechanics Performance Testing is carried out to the PET/ porous carbon hybridized fiber films of preparation using XQ-1A fiber strength and elongation instrument.In thickness
Uniform place, it is 2.5 mm that tunica fibrosa, which is cut into width, and the elongate strip of a length of 50 mm carries out Mechanics Performance Testing at room temperature.
The clamping length of sample is 20 mm, 20 mm/min of tensile speed, each sample testing 5 times.Fiber is measured with screw-thread micrometer
Tie up the thickness of film（mm）.
The data for measuring the front and back mechanical property of etching are as shown in Table 1 and Table 2：
Mechanical performance data before the etching of table 1
| Porous concentration of carbon/% | Strongly/cN | Thickness/mm | Width/mm | Intensity/MPa |
| 0.5 | 15.91 | 0.039 | 2.50 | 1.63 |
| 1.0 | 86.75 | 0.083 | 2.50 | 4.18 |
| 1.5 | 74.77 | 0.112 | 2.50 | 2.67 |
| 2.0 | 89.87 | 0.094 | 2.50 | 3.82 |
| 2.5 | 97.36 | 0.085 | 2.50 | 4.56 |
Mechanical performance data after the etching of table 2
| Porous concentration of carbon/% | Strongly/cN | Thickness/mm | Width/mm | Intensity/MPa |
| 0.5 | 19.80 | 0.066 | 2.50 | 1.20 |
| 1.0 | 84.28 | 0.309 | 2.50 | 1.09 |
| 1.5 | 31.82 | 0.104 | 2.50 | 1.22 |
| 2.0 | 31.62 | 0.099 | 2.50 | 1.28 |
| 2.5 | 86.06 | 0.139 | 2.50 | 2.48 |
By Tables 1 and 2 it is found that before etching, the addition of porous carbon is so that the mechanical property of tunica fibrosa is greatly improved.It is first
Before first etching, fiber film strength is generally gradually to become larger with the increase of porous concentration of carbon, and the addition of porous carbon makes
The strength for obtaining tunica fibrosa becomes larger so that fiber film strength is greatly improved so that its mechanical property becomes excellent.
After etching, equally have been directed to etching after tunica fibrosa carried out the test of tunica fibrosa, although mechanical property be also with
The addition for porous carbon has the tendency that growth, but exposed outside so that the power of tunica fibrosa compared to that can find porous carbon before etching
Performance is learned to be declined.It can be seen that porous carbon is wrapped in the mechanical property that tunica fibrosa can be significantly enhanced in tunica fibrosa,
So that fiber film strength becomes much larger.And after a concentration of 2.0%, it is found that fibre strength is obviously very big.
Four, PET/ porous carbons hybrid material（PET/ porous carbon hybridized fiber films）Specific surface area measurement
The tunica fibrosa for the porous carbon content of difference that five embodiments are spun into, is pinched into coccoid respectively（Conducive to putting spherical shape into
It is measured in test tube）, first weigh the quality of spherical test tube and record, then measure and tunica fibrosa bead is put into spherical shape
In test tube, quality is weighed so that the quality of tunica fibrosa is in 0.3 g or so.Sample is de-gassed, waits degassings to a certain extent
When, it is tested with specific surface instrument, and keep the data on computer.Test results are shown in figure 3.
When the concentration of porous carbon is relatively low, specific surface area is nor very big, but the increase of the concentration with porous carbon
Can be apparent discovery, the specific surface area of porous carbon becomes larger gradually.When porous carbon it is a concentration of 2.0% when, specific surface area
For maximum, specific surface area at this time is best.
Five, PET/ porous carbons hybrid material（PET/ porous carbon hybridized fiber films）Fiber morphology observation
PET fiber is observed using the scanning electron microscope of the model FEI Quanta 250 manufactured by FEI Co. of Czech
The whole pattern of film.With on the careful slave masking foil of tweezers, the PET/ porous carbon hydridization before and after alkaline etching in embodiment one is taken
Tunica fibrosa adheres to above conducting resinl, then then observes pattern, and preserve fibre morphology in metal spraying above again, while using phase
The software answered measures the diameter of fiber, calculates the fibre diameter size prepared by each embodiment.
Fig. 4-Fig. 8 is the scanning electron microscope (SEM) photograph of the PET/ porous carbon hybridized fiber films before and after alkaline etching in embodiment one to five,
In every figure, left side is the scanning electron microscopic picture of the PET/ porous carbon hybridized fiber films before alkaline etching, and right side is after alkaline etching
The scanning electron microscopic picture of PET/ porous carbon hybridized fiber films.
Before observation etching（The left side）Tunica fibrosa pattern, it is known that porous carbon addition so that spinning solution viscosity and electricity
Conductance increases, so that the tunica fibrosa spun out is more uniform, it is denser, so that the overall performance of tunica fibrosa obtains
To raising.After observation etching（The right）Tunica fibrosa pattern, it can be seen that by 5% NaOH weak solutions etching after, have portion
The porous carbon divided exposes, and is attached to the surface of tunica fibrosa, to improve the specific surface area of tunica fibrosa, filtering and absorption
Ability will not make the performance of tunica fibrosa decline by prolonged use.There are one more special in these patterns
The tunica fibrosa of pattern, 1.5% porous carbon content observes occur doughnut in tunica fibrosa after etching under Electronic Speculum, repeat real
Still there is doughnut appearance after testing.The appearance of this phenomenon is need further to study, but this phenomenon is unquestionable
The strainability of tunica fibrosa and absorption property can be made to become more preferable.
The above embodiments are only used to illustrate and not limit the technical solutions of the present invention, although with reference to above-described embodiment to this hair
It is bright to be described in detail, it will be understood by those of ordinary skill in the art that：Still can the present invention be modified or be waited
With replacing, without departing from the spirit or scope of the invention, or any substitutions, the power in the present invention should all be covered
In sharp claimed range.
Claims (6)
- The preparation method of 1.PET/ porous carbon hybrid materials, it is characterised in that carry out according to the following steps successively：First step is to prepare monkey grass based active carbon fiber as porous carbon；Second step is to prepare PET/ porous carbon spinning solutions, and the component and parts by weight of PET/ porous carbon spinning solutions are：16 Part PET, 0.5 to 2.5 part of porous carbon and 81.5 to 83.5 parts of trifluoroacetic acids and mixed solvent made of dichloromethane；Third step is that PET/ porous carbon hybridized fiber films are made in PET spinning solutions using electrostatic spinning machine；Four steps is performed etching to PET/ porous carbon hybridized fiber films using lye, and it is miscellaneous in PET/ porous carbons to increase porous carbon Chemical fibre ties up the exposed amount on membrane fiber surface, obtains PET/ porous carbon hybrid materials.
- 2. the preparation method of PET/ porous carbons hybrid material according to claim 1, it is characterised in that：The second step The specific method for preparing spinning solution includes following sub-step：（1）PET slices is 15-17 hours dry in vacuum drying chamber, and 170 ± 1 DEG C of drying temperature is put into drying after dry It is for use in device；（2）By trifluoroacetic acid and dichloromethane according to volume ratio 1：1 makes mixed solvent；It is positioned over the iodine flask of dried and clean In；Calculating weighs（1）The obtained PET of sub-step is simultaneously added in the mixed solvent, then calculates and weighs porous carbon to mixing In solvent, PET/ porous carbon spinning solutions are made；（3）The rotor of magnetic stirring apparatus is put into after being stirred 4 hours in iodine flask to form uniform spinning solution for use.
- 3. the preparation method of PET/ porous carbons hybrid material according to claim 1, it is characterised in that：The first step Including following sub-step：（1）Pre-oxidation；The monkey grass for being derived from palm living is cut into 3 ± 0.1 centimetres of monkey grass section, by monkey grass Section washs and dries to be placed in Muffle furnace and pre-oxidized, and Pre oxidation is 250 DEG C, and preoxidation time is 3 ± 0.1 hours；（2）Activation；By the monkey grass after pre-oxidation and the zinc chloride in mass ratio 1 as change agent living：1 is mixed；（3）It is soaked in water 24 ± 0.1 hours to the mixture of monkey grass and zinc chloride, monkey grass is made to be mixed with zinc chloride It is even；Then the mixture of monkey grass and zinc chloride is positioned over ventilation to dry 2 ± 0.1 hours, then by monkey grass and chlorine The mixture for changing zinc is placed on heat drying 2 hours in baking oven, and baking oven heating temperature is 120 ± 3 DEG C；It, will be brown after heat drying The mixture of palmitic acid fiber and zinc chloride takes out；（4）The mixture of monkey grass and zinc chloride is carbonized using tube type resistance furnace；Specifically by monkey grass and chlorine After the mixture of change zinc is put into tube type resistance furnace, the temperature in tube type resistance furnace is risen to 800 DEG C, after then being kept for 3 hours again Gradually cooling, waits for that temperature is cooled to room temperature, and takes out the mixture of monkey grass and zinc chloride；（5）Use quality Baidu that the mixture of monkey grass and zinc chloride is impregnated and rinsed than the hydrochloric acid for 20%, until Basic anhydride in the mixture of monkey grass and zinc chloride are neutralized to by hydrochloric acid be in neutrality after, filtered, dried successively With weigh, obtain monkey grass based active carbon fiber.
- 4. the preparation method of PET/ porous carbons hybrid material according to any one of claim 1 to 3, it is characterised in that：The concrete operations of the third step are：The PET/ porous carbon spinning solutions prepared in second step are drawn using syringe, and syringe is mounted on electrostatic spinning machine On, make the piston of syringe and promote that pump is connected and the outlet of syringe is connected by hose with the nozzle of electrostatic spinning machine, The distance between the receiving roll of the nozzle of electrostatic spinning machine and electrostatic spinning machine is adjusted to 16 centimetres；By masking foil it is smooth in receiving roll be used for receive fiber；The spinning voltage of electrostatic spinning machine is set as 25,000 Volt；It it is 100 revs/min by the rotational speed regulation of the receiving roll of electrostatic spinning machine；Start and pump is promoted to promote syringe, keeps PET/ porous Carbon spinning solution is sprayed onto by nozzle on the masking foil in receiving roll, and with the rotation of receiving roll, it is big that thickness is formed in receiving roll In the PET/ porous carbon hybridized fiber films equal to 150 microns；The formation time of PET/ porous carbon hybridized fiber films is 3.5 ± 0.3 Hour.
- 5. the preparation method of PET/ porous carbons hybrid material according to claim 4, it is characterised in that：The concrete operations of the four steps are：The sodium hydroxide solution that mass percent is 5% is first prepared, then PET/ porous carbon hydridization made of clip third step Tunica fibrosa places it in and carries out immersion etching in sodium hydroxide solution, and it is 5 ± 0.2 minutes to impregnate etch period, after impregnating etching It dries, finally by the PET/ porous carbon hybridized fiber films after alkaline etching in valve bag.
- 6. the preparation method of PET/ porous carbons hybrid material according to claim 4, it is characterised in that：In second step, the parts by weight of PET, porous carbon and mixed solvent are following five groups of weights in PET/ porous carbon spinning solutions Measure any group in number：（1）16 parts of PET, 0.5 part of porous carbon, 83.5 parts of trifluoroacetic acids and mixed solvent made of dichloromethane；（2）16 parts of PET, 1.0 parts of porous carbons, 83 parts of trifluoroacetic acids and mixed solvent made of dichloromethane；（3）16 parts of PET, 1.5 parts of porous carbons, 82.5 parts of trifluoroacetic acids and mixed solvent made of dichloromethane；（4）16 parts of PET, 2.0 parts of porous carbons, 82 parts of trifluoroacetic acids and mixed solvent made of dichloromethane；（5）16 parts of PET, 2.5 parts of porous carbons, 81.5 parts of trifluoroacetic acids and mixed solvent made of dichloromethane.
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