CN108486691A - PAN-based carbon fiber precursor pre-oxidation accelerating agent and its application method - Google Patents
PAN-based carbon fiber precursor pre-oxidation accelerating agent and its application method Download PDFInfo
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- CN108486691A CN108486691A CN201810250722.0A CN201810250722A CN108486691A CN 108486691 A CN108486691 A CN 108486691A CN 201810250722 A CN201810250722 A CN 201810250722A CN 108486691 A CN108486691 A CN 108486691A
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- oxidation
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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
- D01F9/12—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
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
- D01F9/225—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles from stabilised polyacrylonitriles
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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
- 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
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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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
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- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The present invention relates to PAN-based carbon fiber precursor pre-oxidation accelerating agent and its application methods, it is 1~60 minute cumyl peroxide that the accelerating agent of the present invention, which refers in 200 DEG C of half-lifes, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, one or several kinds in the peroxide such as di-tert-butyl peroxide, pass through the preparation in polyacryl-nitrile spinning fluid, the spinning of precursor and any of pre-oxidation treatment appoint several addition accelerating agents in the process or are impregnated in accelerator solution, so that polyacrylonitrile fibril Pre oxidation reduces by 10 DEG C or more, preoxidation time reduces 16.7% or more, effectively reduce the energy consumption of carbon fiber preparation process, improve production efficiency, it is simple with operating procedure, it is at low cost, less investment, the advantages that compatible with existing carbon fibre producing facility.
Description
Technical field
The present invention relates to a kind of PAN-based carbon fiber precursor pre-oxidation accelerating agent and its application methods, belong to carbon fiber
Preparation field.
Background technology
Carbon fiber has the characteristics that high specific strength, high ratio modulus, high temperature resistant, corrosion-resistant, electrical and thermal conductivity is good, is advanced multiple
The important reinforcement of condensation material, is widely used in the fields such as space flight and aviation, communications and transportation, building energy and Leisure Sport.
In the preparation of carbon fiber, production and application process, the mechanical property of characterization carbon fiber accurately and timely and its important.Polyacrylonitrile
The preparation process of base carbon fibre includes the basic craft courses such as polymerization, spinning, pre-oxidation and carbonization, wherein pre-oxidize be fiber by
Organic bridge to inorganic conversion, to final carbon fiber performance important.Preoxidation process is also prepared by carbon fiber
Journey takes longest, consumes energy most stages.The pre-oxidation of polyacrylonitrile fibril generally refers to 200~300 DEG C in air atmosphere
At a temperature of carry out long heat treatment a process.Accelerate pre-oxidation speed, reduce Pre oxidation for carbon fiber production
It is energy-saving, improve production efficiency, reduce production cost be of great significance.Chinese patent 200910234656.9 discloses
A kind of polyacrylonitrile fibril impregnates the method to reduce Pre oxidation, improve preoxidation degree in potassium permanganate solution,
But potassium permanganate solution has corrosivity, has an adverse effect to relevant device, while may introduce potassium ion in the fibre
Defect is formed, the performance of carbon fiber is influenced；Chinese patent 201010285139.7 is disclosed with ozone water solution to polyacrylonitrile
Precursor is impregnated to accelerate pre-oxidation speed, reduce Pre oxidation, but ozone sheet is as gas, it is easy to be decomposed into oxygen
Gas is hardly formed stable solution in water, and itself has adverse effect environment.
Invention content
The object of the present invention is to provide a kind of PAN-based carbon fiber precursor pre-oxidation accelerating agent and its application methods.This
Invention is decomposed by peroxide of the selection with higher decomposition teperature, peroxide under polyacrylonitrile fibril Pre oxidation
Free radical is formed, to cause and accelerate the cyano of polyacrylonitrile to form cyclized structure, effectively reduces carbon fiber preparation process
Energy consumption, improve production efficiency.
The present invention provides a kind of PAN-based carbon fiber precursor pre-oxidation accelerating agents, and the accelerating agent is at 200 DEG C
The peroxide that half-life is 1~60 minute.
The peroxide is cumyl peroxide, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, di-t-butyl
One or several kinds in peroxide.
The present invention also provides the application methods of PAN-based carbon fiber precursor pre-oxidation accelerating agent, are spun in polyacrylonitrile
Preparation, the spinning of precursor and any of pre-oxidation treatment of silk liquid appoint several in the process using pre-oxidation accelerating agent.
In the preparation of the polyacryl-nitrile spinning fluid using refer to acrylonitrile polymerization formula in be added pre-oxidation promote
Agent, pre-oxidation accelerating agent quality account for the 0.1~5% of acrylonitrile monemer or polyacrylonitrile quality.
Using referring to by fiber after solidification, traction, washing, oiling, before thermal finalization in the spinning of the precursor,
It is stopped 0.1~5 second in the accelerator solution that mass fraction is 0.1~10%.
The pre-oxidation treatment use refers to, before polyacrylonitrile fibril is pre-oxidized in entrance pre-oxidation furnace,
It is stopped 0.5~5 minute in the accelerator solution that mass fraction is 0.1~10%.
The present invention also provides the application methods of another PAN-based carbon fiber precursor pre-oxidation accelerating agent, poly- third
Before alkene itrile group precursor carries out pre-oxidation treatment in entering pre-oxidation furnace, the accelerator solution for being 0.1~10% in mass fraction
It is middle to stop 0.5~5 minute.
Solvent in the accelerator solution is the organic or inorganic solvent that cannot dissolve poly- propionitrile, and organic solvent is
Ethyl alcohol, acetone, inorganic solvent are water.
The advantages of the present invention：
The present invention passes through in any of the preparation of polyacryl-nitrile spinning fluid, the spinning of precursor and pre-oxidation treatment or several mistakes
Pre-oxidation accelerating agent is used in journey so that polyacrylonitrile fibril Pre oxidation reduces 10 DEG C or more, and preoxidation time shortens
15% or more, the energy consumption of carbon fiber preparation process is effectively reduced, production efficiency is improved, there is operating procedure letter
It is single, at low cost, less investment, it is compatible with existing carbon fibre producing facility the advantages that.
Specific implementation mode
The present invention and its effect are described in further detail with reference to embodiment, it should be pointed out that as described below
Embodiment is intended to be convenient for the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1
(1) preparation of polyacryl-nitrile spinning fluid：By mass fraction, acrylonitrile：Dimethyl sulfoxide (DMSO)：Itaconic acid：Azo two is different
Butyronitrile：Isopropyl benzene hydroperoxide=22：100：0.2：0.1：0.1 is added in polymeric kettle, polymerize at 63 DEG C under stirring condition
Reaction 24 hours；List deaeration 8 hours is taken off under the conditions of vacuum degree is 0.01MPa, temperature is 63 DEG C, obtains spinning solution.
(2) spinning of precursor：Spinning solution is transported to the 3K spinnerets that aperture is 65 microns by metering pump and carries out Wet-spinning
Silk, through solidification, drawing-off, wash, oil, winding obtains polyacrylonitrile fibril after thermal finalization.
(3) it pre-oxidizes：The polyacrylonitrile fibril that step 3) obtains carries out the pre-oxidation of 3 warm area gradient increased temperatures in air atmosphere
Processing, pre-oxidation treatment temperature is respectively 220,240,260 DEG C, and fiber is 20 minutes in each humidity province residence time, total pre-
Oxidation treatment time 60 minutes.
Embodiment 2
(1) preparation of polyacryl-nitrile spinning fluid：By mass fraction, acrylonitrile：Dimethyl sulfoxide (DMSO)：Itaconic acid：Azo two is different
Butyronitrile=22：100：0.2：0.1 is added in polymeric kettle, under stirring condition at 63 DEG C polymerisation 24 hours；In vacuum degree
List deaeration 8 hours is taken off under the conditions of being 63 DEG C for 0.01MPa, temperature, obtains spinning solution.
(2) configuration of maceration extract：Tert-butyl hydroperoxide is configured to the aqueous solution that mass concentration is 2%, is placed in dipping tank
In.
(3) spinning of precursor：Spinning solution is transported to the 3K spinnerets that aperture is 65 microns by metering pump and carries out Wet-spinning
Silk, through solidification, drawing-off, washing, impregnate, oil, winding obtains polyacrylonitrile fibril after thermal finalization, fiber stops in dipping tank
It is 4 seconds to stay the time；
(4) it pre-oxidizes：Step (3) obtains polyacrylonitrile fibril and carries out the pre-oxidation of 4 warm area gradient increased temperatures in air atmosphere
Processing, pre-oxidation treatment temperature is respectively 200,220,240,260 DEG C, and fiber is 15 minutes in each humidity province residence time,
Total 60 minutes pre-oxidation treatment time.
Embodiment 3
(1) preparation of polyacryl-nitrile spinning fluid：With embodiment 2.
(2) configuration of maceration extract：Cumyl peroxide is configured to the acetone soln that mass concentration is 3%, is placed in leaching
In stain slot.
(3) spinning of precursor：Spinning solution is transported to the 3K spinnerets that aperture is 65 microns by metering pump and carries out Wet-spinning
Silk, through solidification, drawing-off, wash, oil, winding obtains polyacrylonitrile fibril after thermal finalization.
(4) it pre-oxidizes：The polyacrylonitrile fibril of step (3) impregnates 2 minutes in the maceration extract of step (2)；After dipping
Polyacrylonitrile fibril is directly entered pre-oxidation furnace, carries out 4 warm area gradient increased temperature pre-oxidation treatments in air atmosphere, at pre-oxidation
It is respectively 190,220,240,270 DEG C to manage temperature, and fiber is 10 minutes in each humidity province residence time, when total pre-oxidation treatment
Between 40 minutes.
Embodiment 4
(1) preparation of polyacryl-nitrile spinning fluid：With embodiment 2.
(2) configuration of maceration extract：Di-tert-butyl peroxide is configured to the ethanol solution that mass concentration is 5%, is placed in
In dipping tank.
(3) spinning of precursor：With embodiment 2.
(4) it pre-oxidizes：The polyacrylonitrile fibril of step (3) impregnates 1 minute in the maceration extract of step (2)；After dipping
Polyacrylonitrile fibril is directly entered pre-oxidation furnace, carries out 3 warm area gradient increased temperature pre-oxidation treatments in air atmosphere, at pre-oxidation
It is respectively 220,240,265 DEG C to manage temperature, and precursor is 15 minutes in each humidity province residence time, total pre-oxidation treatment time 45
Minute.
Comparative example
(1) polyacrylonitrile fibril preparation condition is with embodiment 1, but without isopropyl benzene hydroperoxide in polymerization formula；
(2) polyacrylonitrile fibril carries out 6 warm area gradient increased temperature pre-oxidation treatments, pre-oxidation treatment temperature in air atmosphere
Respectively 200,220,240,260,270 and 280 DEG C, precursor is 12 minutes in each humidity province residence time, at total pre-oxidation
Manage 72 minutes time.
The preoxidation degree of polyacrylonitrile fibre can be characterized by the density of fiber, and the density of pre-oxidized fibers is got over
Height, preoxidation degree are also higher.Using the density for the pre-oxidized fibers that density gradient method testing example and comparative example obtain,
As a result it is listed in table 1.Pre-oxidized fibers preoxidation degree in acquisition is basic quite, and the use for pre-oxidizing accelerating agent is effective
Reduce Pre oxidation and preoxidation time.
Table 1
Claims (8)
1. a kind of PAN-based carbon fiber precursor pre-oxidation accelerating agent, it is characterised in that the accelerating agent refers at 200 DEG C
The peroxide that half-life is 1~60 minute.
2. pre-oxidation accelerating agent according to claim 1, it is characterised in that the peroxide is peroxidating diisopropyl
One or several kinds in benzene, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide.
3. the application method of PAN-based carbon fiber precursor pre-oxidation accelerating agent according to claim 1, feature exist
In any of the preparation of polyacryl-nitrile spinning fluid, the spinning of precursor and pre-oxidation treatment or appoint it is several during using pre-oxidation promote
Into agent.
4. application method according to claim 3, it is characterised in that described to make in the preparation of polyacryl-nitrile spinning fluid
With referring to that pre-oxidation accelerating agent is added in acrylonitrile polymerization formula, pre-oxidation accelerating agent quality accounts for acrylonitrile monemer or polypropylene
The 0.1~5% of nitrile quality.
5. application method according to claim 3, it is characterised in that using referring in the spinning of the precursor, by fiber
After solidification, traction, washing, oil, before thermal finalization, mass fraction be 0.1~10% accelerator solution in stop 0.1~
5 seconds.
6. application method according to claim 3, it is characterised in that using referring to polypropylene in the pre-oxidation treatment
Nitrile precursor stops 0.5 before being pre-oxidized in entering pre-oxidation furnace in the accelerator solution that mass fraction is 0.1~10%
~5 minutes.
7. application method according to claim 5 or 6, it is characterised in that：Solvent in the accelerator solution is not
The organic or inorganic solvent of poly- propionitrile can be dissolved.
8. application method according to claim 7, it is characterised in that：The organic solvent be ethyl alcohol, acetone, it is inorganic molten
Agent is water.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111560666A (en) * | 2020-06-17 | 2020-08-21 | 江苏恒神股份有限公司 | Pre-oxidation method of polyacrylonitrile-based carbon fiber precursor |
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| CN101709517A (en) * | 2009-11-26 | 2010-05-19 | 中复神鹰碳纤维有限责任公司 | PAN-based carbon fiber precursor pre-oxidation pretreatment process |
| CN102704043A (en) * | 2012-06-20 | 2012-10-03 | 北京化工大学 | Preparation method of polyacrylonitrile pre-oxidation fiber and carbon fiber |
| CN103572411A (en) * | 2012-07-31 | 2014-02-12 | 金发科技股份有限公司 | Polyacrylonitrile-based carbon fibers as well as preparation method and application thereof |
| CN104480575A (en) * | 2014-12-26 | 2015-04-01 | 广州金发碳纤维新材料发展有限公司 | Carbon fiber, preparation method of carbon fiber, composite material based on carbon fiber and application |
| JP2016113726A (en) * | 2014-12-16 | 2016-06-23 | 東レ株式会社 | Polyacrylonitrile-based carbon fiber precursor fiber and carbon fiber production method |
| CN106459229A (en) * | 2013-12-23 | 2017-02-22 | 塞特工业公司 | Polyacrylonitrile (pan) polymers with low polydispersity index (pdi) and carbon fibers made therefrom |
-
2018
- 2018-03-26 CN CN201810250722.0A patent/CN108486691B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101709517A (en) * | 2009-11-26 | 2010-05-19 | 中复神鹰碳纤维有限责任公司 | PAN-based carbon fiber precursor pre-oxidation pretreatment process |
| CN102704043A (en) * | 2012-06-20 | 2012-10-03 | 北京化工大学 | Preparation method of polyacrylonitrile pre-oxidation fiber and carbon fiber |
| CN103572411A (en) * | 2012-07-31 | 2014-02-12 | 金发科技股份有限公司 | Polyacrylonitrile-based carbon fibers as well as preparation method and application thereof |
| CN106459229A (en) * | 2013-12-23 | 2017-02-22 | 塞特工业公司 | Polyacrylonitrile (pan) polymers with low polydispersity index (pdi) and carbon fibers made therefrom |
| JP2016113726A (en) * | 2014-12-16 | 2016-06-23 | 東レ株式会社 | Polyacrylonitrile-based carbon fiber precursor fiber and carbon fiber production method |
| CN104480575A (en) * | 2014-12-26 | 2015-04-01 | 广州金发碳纤维新材料发展有限公司 | Carbon fiber, preparation method of carbon fiber, composite material based on carbon fiber and application |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111560666A (en) * | 2020-06-17 | 2020-08-21 | 江苏恒神股份有限公司 | Pre-oxidation method of polyacrylonitrile-based carbon fiber precursor |
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