CN106146836A - A kind of preparation method of conducting polymer/regenerated celulose fibre composite - Google Patents
A kind of preparation method of conducting polymer/regenerated celulose fibre composite Download PDFInfo
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- CN106146836A CN106146836A CN201510182601.3A CN201510182601A CN106146836A CN 106146836 A CN106146836 A CN 106146836A CN 201510182601 A CN201510182601 A CN 201510182601A CN 106146836 A CN106146836 A CN 106146836A
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Abstract
The invention provides a kind of conducting polymer/regenerated celulose fibre composite and preparation method thereof, this composite is with regenerated celulose fibre as template, anion active agent is emulsifying agent, the method using matrix polymerization, by conducting polymer directly at regenerated cellulose surface aggregate, conducting polymer can form fine and close clad on regenerated cellulose surface, and has electric conductivity, prepares conducting polymer/regenerated celulose fibre composite.This can make regenerated celulose fibre have certain conductivity, makes regenerated celulose fibre have conduction or anlistatig effect, expands the range of application of regenerated celulose fibre simultaneously.
Description
Technical field
The present invention relates to a kind of conducing composite material and preparation method thereof, be specifically related to a kind of conducting polymer/regenerated cellulose
Composite material and preparation method thereof.
Background technology
Conducting polymer is owing to having special structure and excellent physicochemical characteristics so that it is electrochromic display device,
Rechargeable battery and fuel cell, the electrode material of ultracapacitor, anti-corrosion of metal material, electromagnetic shielding material, microwave absorption are hidden
Stature material, electroluminescent device positive pole decorative material, sensor, transparent conducting coating, conductive fiber, field effect tube semiconductor
The aspects such as material, polymer light voltaic battery material have extensive and tempting application prospect.Conducting polymer is a kind of difficult
, there is certain difficulty in the polymer of molten infusibility, it is impossible to directly carry out spinning with them in processing, limits its application, because of
This, Recent study person prepare conducting polymer conductive fiber composite material with different fibers and fabric for matrix.Therefore profit
By matrix polymerization method, conducting polymer is deposited on regenerated cellulose surface, while keeping matrix some strength, obtains electric conductivity
Can, can meet special occasions staff for comfortableness, health and protect three aspects needs.
Regenerated celulose fibre is the environmental protection fiber of a kind of function admirable, be utilize cotton linter, timber, bamboo, bagasse,
The regenerated fiber that the natural materials such as phragmites communis are obtained by certain physics and chemical method, the waste and old gurry of its goods can natural degradation.
Active hydroxyl is there is so that regenerated celulose fibre can be with other molecule graft copolymerizations many in producing on regenerated cellulose molecule
Modification, provides broad space for improving the scientific and technological content of regenerated celulose fibre.Regenerated celulose fibre, have soft,
The advantages such as good luster, sucting wet air permeability are good, dyeability is good, are widely used in the fields such as clothing.Utilize matrix polymerization method herein
Conducting polymer is deposited on regenerated celulose fibre surface, on the one hand can utilize the excellent electricity of conduction high polymer, light, magnetic,
The performances such as heat, expand the application of conducting polymer；On the other hand the most significant for exploring personal protection.
At present, the technology of preparing of conductive fiber it has been reported that such as, Xiao Changfa, " preparation method of a kind of conductive fiber and system
Product " (Chinese patent CN1749476A), it is mainly characterized by the method by coating by conductive polymer coated at matrix fiber
Surface, obtains electrically conductive composite fibre.Tanaka etc., are sprayed on fiber sheath jointly by electrically conductive polyaniline and conductive black, preparation
Conductive fiber have the dyeability (US6,413,634 B1) that preferable electric conductivity becomes reconciled.Weili Hu etc., pass through template
Polyaniline is aggregated in Bacterial cellulose surface, prepares polyaniline Bacterial cellulose nano composite membrane, have preferable electric conductivity and
Mechanical property (Hu W, Chen S, Yang Z, et al.Flexible electrically conductive nanocomposite membrane
Based on bacterial cellulose and polyaniline [J] .The Journal of physical chemistry B, 2011,115 (26):
8453-8457.).Coating conducting polymer has preferable electric conductivity, but coat is unstable, and wash durability is poor.
The present invention relates to the preparation method of a kind of conducting polymer/reconstituted cellulose composites so that polymer monomer is at regeneration fibre
There is chemical oxidising polymerisation and then form preferable conducting polymer clad in cellulose fiber surface, has prepared conducting polymer/regeneration
Cellulose fiber dimension conductive composite material.This preparation method avoids difficult the lacking of conducting polymer post-treatment prepared by traditional method
Point, uses directly with regenerated celulose fibre fiber as template, obtains composite in fiber surface polymerization.This composite
There is good electric conductivity and resistance to water performance.This composite may be used for conductive spinning product, solaode, energy storage material,
The aspects such as sensor and water process.
Summary of the invention
The invention provides a kind of conducting polymer/regenerated celulose fibre composite and preparation method thereof, this composite with
Regenerated celulose fibre is template, and anion active agent is emulsifying agent, the method using matrix polymerization, prepares conducting polymer/again
Raw cellulose fiber composite material.This can make regenerated celulose fibre have certain conductivity, makes regenerated celulose fibre have
Conduction or anlistatig effect, expand the range of application of regenerated celulose fibre simultaneously.
The present invention prepares specifically comprising the following steps that of conducting polymer/regenerated celulose fibre composite
(1) regenerated celulose fibre is impregnated pretreatment in organic solvent 0～5 hours, after taking-up, is washed with deionized
Remove the organic solvent of residual, dry, standby.
(2) take a certain amount of anion surfactant and be made into the anionic surfactant solution of 0.05～1mol/L, stirring.
Take again in the regenerated celulose fibre certain mass addition mixed solution that step (1) processes, be subsequently adding monomer, monomer concentration
0.5～2mol/L, stir 1h under room temperature.
(3) adding oxidant in step (2) system, oxidant concentration is 0.6～4mol/L, changes at 0～30 DEG C
Learning oxidation polymerization, stir a period of time, mixing speed controls 1～1000rpm.After reaction terminates, reactant is filtered, depends on
It is colourless that secondary organic solvent, deionized water fully wash to filtrate, 50～120 DEG C dry 10～48h, obtain conducting polymer/
Regenerated celulose fibre composite.
Wherein said regenerated celulose fibre is bamboo fibre, viscose rayon, nitrate fiber, acetate fiber, CUP,
Regenerated cellulose azelon, the one in cellulose carbamate fibre.
Described organic solvent is methanol, ethanol, acetone, ether, chloroform, DMF, N, N-dimethyl second
One or both in amide, dimethyl sulfoxide or N-Methyl pyrrolidone.
Described anion surfactant is sodium lauryl sulphate, sodium hexadecyl sulfate, DBSA and salt thereof,
Cetyl benzenesulfonic acid and salt thereof, ethyoxyl alkyl sodium sulfate, ethyoxyl alkyl ammonium sulfate, polyacrylic acid and salt thereof, dodecane
Base polyethenoxy ether sodium sulfate, sodium soap, alkylpolyoxyethylene carboxylic acid sodium, 1 in sodium methylene bis-naphthalene sulfonate～2
Kind.Solution concentration is 0.05～1mol/L.
Described monomer is pyrroles, aniline, pyrroles, at least one in thiophene.Monomer concentration is 0.5～2mol/L.
Described oxidant is ferric chloride, hydrogen peroxide, Ammonium persulfate., aluminum chloride, potassium permanganate, potassium dichromate, potassium iodate,
In manganese dioxide 1～2 kind.Oxidant concentration is 0.6～4mol/L.
Described conducting polymer includes: polyaniline, polypyrrole, 1 in polythiophene, and derivant～2 kind.
The present invention utilizes the method for matrix polymerization to prepare conducting polymer/regenerated celulose fibre composite, it is to avoid conduction is poly-
The shortcoming that compound should not be processed, saves later stage compound technique, reduces the consumption of the energy.Matrix polymerization method has efficiency simultaneously
Height, the advantages such as equipment is simple, easy to operate, the most large-scale commercial production.The more important thing is this conducting polymer/regeneration
Cellulose fiber composite material has good electric conductivity and wash durability, has the biggest potential using value.
Accompanying drawing explanation
Fig. 1 is embodiment 1 viscose rayon shape appearance figure (scanning electron micrographs).
Fig. 2 is the polyaniline obtained by embodiment 1/viscose rayon composite shape appearance figure (scanning electron micrographs).
Fig. 3 is the polyaniline obtained by making an excessive case more excessive example 2/viscose rayon composite shape appearance figure (scanning electron micrographs).
Fig. 4 is the polyaniline obtained by embodiment 2/viscose rayon composite infrared analysis figure.
Fig. 5 is the polyaniline obtained by embodiment 2/viscose rayon conductivity of composite material and washing times graph of a relation.
Detailed description of the invention
Below by way of specific embodiment for further illustrating the method that the present invention describes, it is not intended that the present invention is limited to
These embodiments.
Embodiment 1:
A kind of conducting polymer/regenerated celulose fibre composite process, comprises the steps:
(1) 1kg viscose rayon is impregnated the most ultrasonic pretreatment 2 hours, then take out, be washed with deionized and remove
Go residual acetone, 60 DEG C of drying, standby.
(2) take a certain amount of sodium hexadecyl sulfate and be made into the sodium hexadecyl sulfate solution of 0.3mol/L, stirring.Take place again
The viscose rayon certain mass of reason adds in mixed solution, is subsequently adding through aniline monomer, monomer concentration 0.5mol/L, room
2h is stirred under temperature.
(3) adding Ammonium persulfate. in above-mentioned system, ammonium persulfate concentrations is 0.8mol/L, is at room temperature polymerized, stirs
Mixing a period of time, mixing speed controls at 500rpm.Reaction terminate after, by reactant filter, successively with ethanol, go from
It is colourless that sub-water fully washs to filtrate, dries 24h, obtains polyaniline/viscose rayon composite for 60 DEG C.
Polyaniline/viscose rayon composite obtained by preparation, Fig. 1 is viscose rayon, it can be seen that fibre diameter is about 13
Micron.Fig. 2 is polyaniline/viscose rayon composite, and as seen from the figure, fibre diameter is about 15 microns, and polyaniline exists
Fiber surface forms fine and close clad.
Embodiment 2:
A kind of conducting polymer/regenerated celulose fibre composite process, comprises the steps:
(1) 1kg viscose rayon is impregnated the most ultrasonic pretreatment 3 hours, then take out, be washed with deionized and remove
Go residual ethanol, 60 DEG C of drying, standby.
(2) take a certain amount of DBSA and be made into the dodecylbenzenesulfonic acid solution of 1mol/L, stirring.Take place again
The viscose rayon certain mass of reason adds in mixed solution, is subsequently adding through purifying aniline monomer, monomer concentration 0.5mol/L,
2h is stirred under room temperature.
(3) adding Ammonium persulfate. in above-mentioned system, ammonium persulfate concentrations is 0.6mol/L, is at room temperature polymerized, stirs
Mixing a period of time, mixing speed controls at 500rpm.Reaction terminate after, by reactant filter, successively with ethanol, go from
It is colourless that sub-water fully washs to filtrate, dries 24h, obtains polyaniline/viscose rayon composite for 60 DEG C.
Polyaniline/viscose rayon composite obtained by preparation, Fig. 3 is polyaniline/viscose rayon composite, dodecyl
Benzenesulfonic acid forms the thicker clad of densification as emulsifying agent polymerization polyaniline at fiber surface.Fig. 4 is infrared test, and a is pure
The infrared curve of viscose rayon, b is DBSA is polymerized the infrared curve of polyaniline as emulsifying agent, and c is polyaniline
The infrared curve of/viscose rayon composite, infrared it is also seen that polyaniline has well been coated with viscose rayon.Fig. 5 is poly-
Aniline/viscose rayon conductivity of composite material test, it can be seen that polyaniline/viscose rayon composite has the most water-fast
Washing property, after washing 40 times, conductivity is basically unchanged, and stills remain in 10-1S/cm。
Embodiment 3:
A kind of conducting polymer/regenerated celulose fibre composite process, comprises the steps:
(1) 1kg viscose rayon is impregnated the most ultrasonic pretreatment 2 hours, then take out, be washed with deionized and remove
Go residual acetone, 60 DEG C of drying, standby.
(2) take a certain amount of dodecylbenzene sodium sulfonate and be made into the dodecylbenzene sodium sulfonate solution of 0.3mol/L, stirring.Again
The viscose rayon certain mass taking process adds in mixed solution, is subsequently adding pyrrole monomer, monomer concentration 0.8mol/L, room
2h is stirred under temperature.
(3) adding ferric chloride in above-mentioned system, ferric chloride concentration is 0.6mol/L, is at room temperature polymerized, stirs
Mixing a period of time, mixing speed controls at 500rpm.Reaction terminate after, by reactant filter, successively with ethanol, go from
It is colourless that sub-water fully washs to filtrate, dries 24h, obtains polypyrrole/viscose rayon composite for 60 DEG C.
Embodiment 4:
A kind of conducting polymer/regenerated celulose fibre composite process, comprises the steps:
(1) 1kg CUP is impregnated the most ultrasonic pretreatment 1 hour, then take out, be washed with deionized and remove
Go residual acetone, 60 DEG C of drying, standby.
(2) take a certain amount of sodium lauryl sulphate and be made into the sodium dodecyl sulfate solution of 0.5mol/L, stirring.Take place again
The viscose rayon certain mass of reason adds in mixed solution, is subsequently adding thiophene monomer, and monomer concentration 0.6mol/L, under room temperature
Stirring 2h.
(3) adding aluminum chloride in above-mentioned system, aluminum trichloride concentration is 0.6mol/L, is at room temperature polymerized, stirs
Mixing a period of time, mixing speed controls at 600rpm.Reaction terminate after, by reactant filter, successively with ethanol, go from
It is colourless that sub-water fully washs to filtrate, dries 24h, obtains polythiophene amine/CUP composite for 60 DEG C.
Claims (7)
1. a preparation method for conducting polymer/regenerated celulose fibre composite, it comprises the steps:
(1) regenerated celulose fibre is impregnated pretreatment in organic solvent 0～5 hours, after taking-up, is washed with deionized
Remove the organic solvent of residual, dry, standby.
(2) take a certain amount of anion surfactant and be made into the anionic surfactant solution of 0.05～1mol/L, stirring.
Take again in the regenerated celulose fibre certain mass addition mixed solution that step (1) processes, be subsequently adding monomer, monomer concentration
0.5～2mol/L, stir 1h under room temperature.
(3) adding oxidant in step (2) system, oxidant concentration is 0.6～4mol/L, changes at 0～30 DEG C
Learning oxidation polymerization, stir a period of time, mixing speed controls 1～1000rpm.After reaction terminates, reactant is filtered, depends on
It is colourless that secondary organic solvent, deionized water fully wash to filtrate, 50～120 DEG C dry 10～48h, obtain conducting polymer/
Regenerated celulose fibre composite.
2. preparation method as claimed in claim 1, described regenerated celulose fibre is bamboo fibre, viscose rayon, nitrate
Fiber, acetate fiber, CUP, regenerated cellulose azelon, the one in cellulose carbamate fibre.
3. preparation method as claimed in claim 1, described organic solvent is methanol, ethanol, acetone, ether, chloroform, N,
One or both in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide or N-Methyl pyrrolidone.
4. preparation method as claimed in claim 1, described anion surfactant is sodium lauryl sulphate, hexadecane
Base sodium sulfate, DBSA and salt thereof, cetyl benzenesulfonic acid and salt thereof, ethyoxyl alkyl sodium sulfate, alkyl ethoxylate
Base ammonium sulfate, polyacrylic acid and salt thereof, alkylpolyoxyethylene sodium sulfate, sodium soap, alkylpolyoxyethylene
Carboxylic acid sodium, 1 in sodium methylene bis-naphthalene sulfonate～2 kind.Solution concentration is 0.05～1mol/L.
5. preparation method as claimed in claim 1, described monomer is pyrroles, aniline, pyrroles, at least one in thiophene.
Monomer concentration is 0.5～2mol/L.
6. preparation method as claimed in claim 1, described oxidant is ferric chloride, hydrogen peroxide, Ammonium persulfate., trichlorine
Change aluminum, potassium permanganate, potassium dichromate, potassium iodate, 1 in manganese dioxide～2 kind.Oxidant concentration is 0.6～4mol/L.
7. conducting polymer includes as claimed in claim 1: polyaniline, polypyrrole, polythiophene, and derivant.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108492908A (en) * | 2018-03-15 | 2018-09-04 | 青岛科技大学 | A kind of preparation method of optical activity Cellulose nanocrystal body/conductive conjugated polymer composite membrane |
| CN110079958A (en) * | 2019-03-20 | 2019-08-02 | 武汉飞帛丝科技有限公司 | A kind of conductive fabric automatic producing device and method |
| CN110130110A (en) * | 2019-04-18 | 2019-08-16 | 浙江理工大学 | A kind of preparation method for the conductive regenerated celulose fibre being related to surface aggregate |
| CN110655768A (en) * | 2017-12-06 | 2020-01-07 | 雷珊珊 | Polylactic acid fiber fused polypyrrole material and preparation method thereof |
| CN111171289A (en) * | 2020-01-13 | 2020-05-19 | 福建农林大学 | TEMPO oxidized cellulose/PEDOT polymer and preparation method and application thereof |
| CN113943462A (en) * | 2021-11-10 | 2022-01-18 | 江阴市海江高分子材料有限公司 | Conductive polymer composite material and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655768A (en) * | 2017-12-06 | 2020-01-07 | 雷珊珊 | Polylactic acid fiber fused polypyrrole material and preparation method thereof |
| CN108492908A (en) * | 2018-03-15 | 2018-09-04 | 青岛科技大学 | A kind of preparation method of optical activity Cellulose nanocrystal body/conductive conjugated polymer composite membrane |
| CN108492908B (en) * | 2018-03-15 | 2019-07-12 | 青岛科技大学 | A kind of preparation method of optical activity Cellulose nanocrystal body/conductive conjugated polymer composite membrane |
| CN110079958A (en) * | 2019-03-20 | 2019-08-02 | 武汉飞帛丝科技有限公司 | A kind of conductive fabric automatic producing device and method |
| CN110079958B (en) * | 2019-03-20 | 2021-06-11 | 武汉飞帛丝科技有限公司 | Automatic production equipment and method for conductive cloth |
| CN110130110A (en) * | 2019-04-18 | 2019-08-16 | 浙江理工大学 | A kind of preparation method for the conductive regenerated celulose fibre being related to surface aggregate |
| CN111171289A (en) * | 2020-01-13 | 2020-05-19 | 福建农林大学 | TEMPO oxidized cellulose/PEDOT polymer and preparation method and application thereof |
| CN113943462A (en) * | 2021-11-10 | 2022-01-18 | 江阴市海江高分子材料有限公司 | Conductive polymer composite material and preparation method and application thereof |
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Application publication date: 20161123 |