CN107034586A - A kind of poly butyric ester/polypyrrole composite conducting nano fibrous membrane and preparation method thereof - Google Patents
A kind of poly butyric ester/polypyrrole composite conducting nano fibrous membrane and preparation method thereof Download PDFInfo
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- CN107034586A CN107034586A CN201710280117.3A CN201710280117A CN107034586A CN 107034586 A CN107034586 A CN 107034586A CN 201710280117 A CN201710280117 A CN 201710280117A CN 107034586 A CN107034586 A CN 107034586A
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- polypyrrole
- butyric ester
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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
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
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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
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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
- D04H1/70—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
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
- D10B2331/041—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET] derived from hydroxy-carboxylic acids, e.g. lactones
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/14—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
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Abstract
The present invention discloses a kind of poly butyric ester/polypyrrole composite conducting nano fibrous membrane and preparation method thereof, belongs to polymeric material field.This method includes procedure below：Polypyrrole is doped processing first, then adds it to ultrasonic disperse is carried out in solvent；Poly butyric ester is added in solvent again and stirred to being completely dissolved；Two kinds of solution are mixed with certain proportion again, shaken up, the spinning solution of stable homogeneous is formed, electrostatic spinning is carried out, high-pressure electrostatic 10~30kV of adjustable range injects 0.05~0.3ml/h of flow rate pump, receives 10~20cm of distance.Preparation method process of the present invention is simple, and prepared poly butyric ester/polypyrrole composite nano fiber film has good physical and mechanical properties, biocompatibility, biological degradability and good electric conductivity.
Description
Technical field
The invention belongs to polymeric material field, and in particular to a kind of poly butyric ester/polypyrrole composite conducting nanometer
Tunica fibrosa and preparation method thereof.
Background technology
Electrostatic spinning is a kind of effective production technology directly perceived that nano-scale fiber is prepared using high-voltage electrostatic field, in height
Polymer solution or extensional melt in the presence of piezoelectricity field force, attenuate, finally solidify to form diameter and received at tens nanometers to hundreds of
Nanofiber in the range of rice.Method of electrostatic spinning prepare nanofiber specific surface area it is big, porosity is high, pliability good, wide
It is general to be applied to the various fields such as organizational project, medical carrier, filtering material, sensor, catalyst.Due to this preparation Nanowire
The features such as technology of dimension has simple, cheap, efficient and environmentally friendly, by the extensive concern of scientific research personnel, and is developed rapidly.
Polyhydroxyalkanoate (PHB) is that a kind of intracellular polyester is main by Microbe synthesis, is the natural height of thermoplastics type
Molecular biosciences material.PHB structural uniformity is high, with high crystalline, optical activity and piezoelectric properties, is the poly- of stereoregular
Compound.The numerous excellent characteristics of PHB, such as environment-friendly, mechanical performance is excellent, biodegradable, crystallinity is high, imparts it
Different application in various fields.The poly butyric ester fiber prepared with electrospinning process has fibre diameter small, compares table
The characteristics of area is high, and with more preferable biocompatibility and biological degradability, support, wound bag that can be as organizational project
Prick the carrier of material and insoluble drug release.Polypyrrole is a kind of conducting polymer synthetic material.Electric conductivity as existing metal, but it is simultaneous
Have the machinability and excellent environmental stability of plastics, gained great popularity in conducting polymer composite field.Due to its monomer valency
Lattice are cheap, synthesis technique is simple, possess high conductivity and adjustable potential and potential dissolving, melt-processed characteristic, in electromagnetism
The field such as shielding material and antistatic, anticorrosive coating, gas sensor, special seperation film is with a wide range of applications.But
It is that the spinning property of polypyrrole is poor, independent spinning is difficult to the nanofiber to form continuous-stable, it usually needs add other and gather
Compound carries out blend spinning.If polypyrrole be combined first with poly butyric ester, electrostatic spinning is then carried out again, then
It is expected to obtain the PHB composite nano-fiber membranes with excellent conductive performance, PHB nanofibers will be greatly expanded in bio-medical
Application in field.
The content of the invention
It is an object of the invention to provide a kind of poly butyric ester/polypyrrole composite conducting nano fibrous membrane and its preparation side
Method, the poly butyric ester prepared in this way/polypyrrole composite nano fiber film has good physical and mechanical properties, biology
Compatibility, biological degradability and good electric conductivity.The present invention is realized by the following technical scheme.A kind of poly- hydroxyl
Polypyrrole is doped processing by butyrate/polypyrrole composite conducting nano fibrous membrane and preparation method thereof, this method first, then
Add it to and ultrasonic disperse is carried out in solvent；Poly butyric ester is added in solvent again and stirred to being completely dissolved；Again will
Two kinds of solution are mixed with certain proportion, shaken up, and form the spinning solution of stable homogeneous, poly butyric is prepared by electrostatic spinning
Ester/polypyrrole composite conducting nano fibrous membrane, this method is characterized in that including procedure below：
(1) polypyrrole is mixed for 1: 1~1: 6 in molar ratio with dopant, is dispersed in 100ml deionized water
In, 30~60 DEG C of constant temperature, sealing stirring 4-12h makes two kinds of raw materials fully contact and react, then carries out being filtered by vacuum while not
Disconnected deionized water rinsing, then vacuum drying, the polypyrrole adulterated；
(2) polypyrrole of doping is added in solvent dimethylformamide at room temperature, ultrasonically treated 2h is configured to matter
Measure the solution I that volume fraction is 0.1~5%；
(3) molecular weight is dissolved in solvent for 20~500,000 poly butyric ester at room temperature, magnetic agitation 6h matches somebody with somebody
The solution II that quality volume fraction is 1~5% is made；
(4) solution II that the solution I and step (2) obtained step (2) is obtained is by volume 1: 10~5: 10 mixing,
Ultrasonic agitation obtains spinning solution in 2 hours；
(5) spinning solution for obtaining step (4) is added in syringe, and is fixed on micro-injection pump, is adopted
Received with roller, high-pressure electrostatic 10~30kV of adjustable range, injection 0.05~0.3ml/h of flow rate pump, reception distance 10~
20cm, obtains a diameter of 200~500nm composite conductings nano fibrous membrane.
Preparation method process of the present invention is simple, and prepared poly butyric ester/polypyrrole composite nano fiber film has
Good physical and mechanical properties, biocompatibility, biological degradability and good electric conductivity.
Embodiment
Embodiment 1：
Polypyrrole is mixed for 1: 1 in molar ratio with hydrochloric acid, is dispersed in 100ml deionized water, 30 DEG C of constant temperature,
Sealing stirring 4h, makes two kinds of raw materials fully contact and react, and then carries out being filtered by vacuum while constantly use deionized water rinsing, then
Vacuum drying, the polypyrrole adulterated；The polypyrrole of doping is added in solvent dimethylformamide at room temperature, ultrasound
2h is handled, the solution I that quality volume fraction is 0.1% is configured to；At room temperature by molecular weight be 200,000 poly butyric ester
It is dissolved in chloroform, magnetic agitation 6h, is configured to the solution II that quality volume fraction is 3%；Solution I and solution II are pressed into volume
Than being mixed for 1: 10, ultrasonic agitation obtains spinning solution in 2 hours；Spinning solution is added in syringe, and is fixed in
On micro-injection pump, received using roller, high-pressure electrostatic adjustable range 10kV, inject flow rate pump 0.3ml/h, receive distance
10cm, obtains a diameter of 500nm composite conductings nano fibrous membrane.
Embodiment 2：
Polypyrrole is mixed for 1: 2 in molar ratio with sulfuric acid, is dispersed in 100ml deionized water, 40 DEG C of constant temperature,
Sealing stirring 8h, makes two kinds of raw materials fully contact and react, and then carries out being filtered by vacuum while constantly use deionized water rinsing, then
Vacuum drying, the polypyrrole adulterated；The polypyrrole of doping is added in solvent dimethylformamide at room temperature, ultrasound
2h is handled, the solution I that quality volume fraction is 0.5% is configured to；At room temperature by molecular weight be 300,000 poly butyric ester
It is dissolved in trifluoroacetic acid, magnetic agitation 6h, is configured to the solution II that quality volume fraction is 5%；Solution I and solution II are pressed
Volume ratio is 5: 10 mixing, and ultrasonic agitation obtains spinning solution in 2 hours；Spinning solution is added in syringe, and consolidated
It is scheduled on micro-injection pump, is received using roller, high-pressure electrostatic adjustable range 15kV injects flow rate pump 0.15ml/h, connect
Receive apart from 15cm, obtain a diameter of 400nm composite conductings nano fibrous membrane.
Embodiment 3：
Polypyrrole is mixed for 1: 4 in molar ratio with dialkyl benzene sulfonic acids, is dispersed in 100ml deionized water,
50 DEG C of constant temperature, sealing stirring 10h, two kinds of raw materials is fully contacted and is reacted, then carry out be filtered by vacuum and meanwhile constantly spend from
Sub- water is rinsed, then vacuum drying, the polypyrrole adulterated；The polypyrrole of doping is added to dimethylformamide at room temperature
In solvent, ultrasonically treated 2h is configured to the solution I that quality volume fraction is 2%；At room temperature by molecular weight be 400,000 poly- hydroxyl
Base butyrate is dissolved in chloroform, magnetic agitation 6h, is configured to the solution II that quality volume fraction is 1%；By solution I and solution
II is by volume 3: 10 mixing, and ultrasonic agitation obtains spinning solution in 2 hours；Spinning solution is added in syringe, and will
It is fixed on micro-injection pump, is received using roller, high-pressure electrostatic adjustable range 20kV, injects flow rate pump 0.1ml/h,
Receive apart from 20cm, obtain a diameter of 300nm composite conductings nano fibrous membrane.
Embodiment 4：
Polypyrrole is mixed for 1: 6 in molar ratio with sulfosalicylic acid, is dispersed in 100ml deionized water, it is permanent
60 DEG C of temperature, sealing stirring 12h, makes two kinds of raw materials fully contact and react, and then carries out being filtered by vacuum while constantly using deionization
Water is rinsed, then vacuum drying, obtains the polypyrrole of sulfosalisylic acid doping；At room temperature by the polypyrrole of sulfosalisylic acid doping
It is added in solvent dimethylformamide, ultrasonically treated 2h, is configured to the solution I that quality volume fraction is 2%；At room temperature will
Molecular weight is dissolved in dimethylformamide for 500,000 poly butyric ester, and magnetic agitation 6h is configured to quality volume fraction
For 3% solution II；It is by volume 2: 10 mixing by solution I and solution II, ultrasonic agitation obtains spinning solution in 2 hours；Will
Spinning solution is added in syringe, and is fixed on micro-injection pump, is received using roller, high-pressure electrostatic regulation
Scope 30kV, injects flow rate pump 0.05ml/h, receives apart from 20cm, obtains a diameter of 200nm composite conductings nano fibrous membrane.
Claims (4)
1. a kind of poly butyric ester/polypyrrole composite conducting nano fibrous membrane, it is characterized in that, it is by poly butyric ester and gathers
Pyrroles's first dispersion mixing, then composite nano-fiber membrane is prepared by electrostatic spinning in a solvent.
2. the preparation method of a kind of poly butyric ester/polypyrrole composite conducting nano fibrous membrane, it is characterized in that it is including following
Step：
(1) polypyrrole is mixed for 1: 1~1: 6 in molar ratio with dopant, be dispersed in 100ml deionized water, it is permanent
30~60 DEG C of temperature, sealing stirring 4-12h, makes two kinds of raw materials fully contact and react, and then carries out being filtered by vacuum and constantly uses simultaneously
Deionized water rinsing, then vacuum drying, the polypyrrole adulterated；
(2) polypyrrole of doping is added in solvent dimethylformamide at room temperature, ultrasonically treated 2h is configured to mass body
Fraction is 0.1~5% solution I；
(3) molecular weight is dissolved in solvent for 20~500,000 poly butyric ester at room temperature, magnetic agitation 6h is configured to
Quality volume fraction is 1~5% solution II；
(4) solution II that the solution I and step (2) obtained step (2) is obtained is by volume 1: 10~5: 10 mixing, ultrasound
Stirring obtains spinning solution in 2 hours；
(5) spinning solution for obtaining step (4) is added in syringe, and is fixed on micro-injection pump, using rolling
Cylinder is received, high-pressure electrostatic 10~30kV of adjustable range, injects 0.05~0.3ml/h of flow rate pump, receives 10~20cm of distance,
Obtain a diameter of 200~500nm composite conductings nano fibrous membrane.
3. a kind of preparation method of poly butyric ester according to claim 2/polypyrrole composite conducting nano fibrous membrane,
It is characterized in that：Described dopant can be one kind in hydrochloric acid, sulfuric acid, sulfosalicylic acid, dialkyl benzene sulfonic acids.
4. a kind of preparation method of poly butyric ester according to claim 2/polypyrrole composite conducting nano fibrous membrane,
It is characterized in that：Described solvent can be one kind or two kinds of solvents in chloroform, dimethylformamide, trifluoroacetic acid
Mixture.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114775164A (en) * | 2022-06-21 | 2022-07-22 | 山东华冠智能卡有限公司 | RFID electronic tag substrate capable of being repeatedly folded and preparation method thereof |
| CN116198201A (en) * | 2022-11-24 | 2023-06-02 | 西南交通大学 | Fiber structure biological PHB-based flexible conductive film, preparation and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102102278A (en) * | 2011-02-21 | 2011-06-22 | 浙江理工大学 | Preparation method of silk fibroin-poly(hydroxybutyrate-hydroxyvalerate) composite fiber membrane |
| CN102355904A (en) * | 2008-11-07 | 2012-02-15 | Uab研究基金会 | Endothelium mimicking nanomatrix |
| CN103572408A (en) * | 2012-08-07 | 2014-02-12 | 嘉兴学院 | Core-shell structure electroactive composite fibers and preparation method of tissue engineering scaffold |
| CN104745819A (en) * | 2013-12-27 | 2015-07-01 | 中国科学院宁波材料技术与工程研究所 | Method for using conducting polymer nano spinning for recovery of metals from electronic waste |
-
2017
- 2017-04-21 CN CN201710280117.3A patent/CN107034586A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102355904A (en) * | 2008-11-07 | 2012-02-15 | Uab研究基金会 | Endothelium mimicking nanomatrix |
| CN102102278A (en) * | 2011-02-21 | 2011-06-22 | 浙江理工大学 | Preparation method of silk fibroin-poly(hydroxybutyrate-hydroxyvalerate) composite fiber membrane |
| CN103572408A (en) * | 2012-08-07 | 2014-02-12 | 嘉兴学院 | Core-shell structure electroactive composite fibers and preparation method of tissue engineering scaffold |
| CN104745819A (en) * | 2013-12-27 | 2015-07-01 | 中国科学院宁波材料技术与工程研究所 | Method for using conducting polymer nano spinning for recovery of metals from electronic waste |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114775164A (en) * | 2022-06-21 | 2022-07-22 | 山东华冠智能卡有限公司 | RFID electronic tag substrate capable of being repeatedly folded and preparation method thereof |
| CN116198201A (en) * | 2022-11-24 | 2023-06-02 | 西南交通大学 | Fiber structure biological PHB-based flexible conductive film, preparation and application |
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Application publication date: 20170811 |