CN110130095A - A kind of high-performance aromatic polymer fiber and preparation method - Google Patents
A kind of high-performance aromatic polymer fiber and preparation method Download PDFInfo
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- CN110130095A CN110130095A CN201910364958.1A CN201910364958A CN110130095A CN 110130095 A CN110130095 A CN 110130095A CN 201910364958 A CN201910364958 A CN 201910364958A CN 110130095 A CN110130095 A CN 110130095A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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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
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
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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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic System
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
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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
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
Abstract
The present invention provides a kind of preparation methods of high-performance aromatic polymer fiber, the described method comprises the following steps: using the as-spun fibre of aromatic polymer as raw material, be dipped in the solution containing transition metal ions, react, drying, heat treatment to get.The aromatic polymer fiber being prepared using this method can form uniform polygamy bit architecture, excellent combination property with metal ion, and tensile property, compression performance, thermal stability, uvioresistant ability are significantly increased.Using above-mentioned aromatic polymer fiber, its epoxy resin composite material has further been made in the present invention, and the interlaminar shear strength of the composite material is significantly improved, had a good application prospect.
Description
Technical field
The invention belongs to field of polymer composite material, and in particular to a kind of high-performance aromatic polymer fiber and preparation
Method.
Background technique
As one kind of high-performance fiber, aromatic polymer fiber (abbreviation aramid fiber) is resistance to its excellent mechanical property
It is hot, it is widely used in the every field such as national military project.Compared to carbon fiber, the advantage of aramid fiber be it is light, as aircraft,
Its weight can be significantly reduced when the large-scale composite materials structure material such as airship.But, it is contemplated that the reality of composite material is answered
With aspect, there is some disadvantages compared to carbon fiber for aramid fiber, and main includes two aspects, and first is lower composite material circle
The compression performance of face performance and fiber, second is that the lower heat resistance of fiber.
Aramid III fiber is that 2- (4- aminophenyl) -5- aminobenzimidazole (PABZ) is used as a kind of diamine monomer, copolymerization
To high-performance aramid fiber obtained in PPTA segment, N atom has lone pair electrons on the C=N in benzimidazole structure, can
To occupy transition metal ions, such as Fe3+And Cu2+Deng outer layer unoccupied orbital, complexation reaction occurs with it.This coordination is mutual
Effect is introduced between fiber macromolecular chain, it may be desirable that promotes its properties.But how this Coordination interaction to be drawn
Enter that there is three challenges into fibrous inside: (1) aromatic polymer usually has numerous benzene ring structures to be conjugated to be formed, be aobvious first
The stiff chain structure of work；And to realize the Coordination interaction between aramid fiber macromolecular chain, need metal ion big with difference simultaneously
Benzo imidazole group occurs complexation reaction and forms polygamy bit architecture between strand, and this requires aromatic polymers to carry out centainly
Conformation Transition reaches this structure, and generally rigid segment macromolecular is difficult to be moved, and macromolecular chain is difficult to happen conformation and turns
Become and realize that benzimidazole group is simultaneously with a metal ion there is a phenomenon where being coordinated on different chains, so cannot achieve polygamy position
The introducing of structure.And what is more commonly obtained is then that metal ion and a benzimidazole group are coordinated there is a phenomenon where single；So
How to realize that from multiple benzimidazole groups on different macromolecular chains complexation reaction occurs simultaneously for metal ion is a problem；
It (2) is metal ion, especially heavy metal ion, the influence to the thermal stability of aromatic polymer structure；Generally, it is considered that often
The heavy metal ion seen, such as Fe3+, meeting catalytic polymer is degraded under the high temperature conditions, and aromatic polymer macromolecular
Fiber usually requires certain heat treatment to reach oriented crystalline physically；It (3) is this Coordination interaction in fibre
Homogeneity question inside dimension, whether this depends primarily on metal ion and is uniformly distributed and reacts in fibrous inside；
Due to aromatic polymer finished fiber crystallinity usually with higher, inside solid degree is higher, seriously hinders metal
The diffusion of ion internally is more likely to the state that a large amount of metal ion concentrates on fiber skin region occur, this obviously can not
Realize the promotion of its lateral performance, compression performance and hot property.
The present inventor provides in research before a kind of prepares high composite performance aromatic polymer containing benzimidazole
The method (CN106758136A) of fiber, i.e., will first contain benzimidazole aromatic polymer fiber static immersing or dynamic is continuous logical
Cross reaction and drying in mixed solution made of organic polar solvent and water containing transition metal ions, then again static immersing or
Dynamic, which is continued through, reacts vacuum drying in the ethanol solution of the aminated compounds containing polyamino.But this method will be fragrant
Race's polymer finished fiber static immersing or dynamic continue through the organic polar solvent containing transition metal ions and water is made
Mixed solution in, reaction, seriously hinder the diffusion of metal ion internally, and then affect coordination of metal ion in fiber
Internal is uniformly distributed；Moreover, finished fiber crystallinity is higher, molecular motion is difficult, is unfavorable for the transformation of macromolecular conformation, nothing
Method realizes that complexation reaction occurs from multiple benzimidazole groups on different macromolecular chains simultaneously simultaneously for metal ion, realizes coordination
Crosslinking；In addition, its transition metal ions for using, Fe3+Contain catalytic degradation Deng to polymer.So this contains benzimidazole
Aromatic polymer fiber is not met by demand on compression performance, thermal stability.
So it is urgent to provide a kind of cutting performance, compression performance, the better aromatic polymer fibers of thermal stability at present
And its composite material.
Summary of the invention
The purpose of the present invention is to provide a kind of cutting performance, compression performance, the better aromatic polymers of thermal stability
Fiber and preparation method thereof.
The present invention provides a kind of preparation methods of high-performance aromatic polymer fiber, and the method includes following steps
It is rapid: it using the as-spun fibre of aromatic polymer as raw material, is dipped in the solution containing transition metal ions, reacts, drying,
Heat treatment to get.
Further, the transition metal ions is selected from Cu2+；
Preferably, the transition metal ions is by CuCl2、CuSO4One of or a variety of offers.
Further, the aromatic polymer is the aromatic polymer containing benzimidazole structure, preferably contains benzo
The polyamide of glyoxaline structure or polyimides containing benzimidazole structure；
And/or the as-spun fibre is as made from wet spinning process；
And/or the solvent in the solution is selected from the mixed solvent of water and organic solvent；
And/or the mass fraction of transition metal ions is 0.01-30% in the solution；
The mode of the heat treatment are as follows: under 360 DEG C, nitrogen atmosphere carry out no-station pole canopy static heat treatment, or, in 380 DEG C,
Hot-stretch containing tension is carried out under nitrogen atmosphere.
Further, the immersion mode is static immersing, and the reaction temperature is 50-90 DEG C, and the reaction time is
5-300min, it is preferable that the reaction temperature is 60-80 DEG C, and the reaction time is 120-300min；
Or, the immersion mode is that dynamic continues through, the reaction temperature is 60-95 DEG C, and the reaction time is
0.1-2min, it is preferable that the reaction temperature is 60-95 DEG C, and the reaction time is 0.1-0.3min.
Further, the aromatic polymer is by paraphthaloyl chloride, 2- (4- aminophenyl) -5- amino benzo
Imidazoles is what polymerizable raw material obtained；
Or, being obtained by paraphthaloyl chloride, 2- (4- aminophenyl) -5- aminobenzimidazole and p-phenylenediamine for polymerizable raw material
It arrives；
Or, 3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 2- (4- aminophenyl) -5- aminobenzimidazole are polymerizable raw material by 3
It obtains.
Further, the paraphthaloyl chloride: (p-phenylenediamine+2- (4- aminophenyl) -5- aminobenzimidazole)
Molar ratio is 1:1, wherein p-phenylenediamine and 2- (4- aminophenyl) -5- aminobenzimidazole) molar ratio be (0~7): (3~
10)；
Or, described 3, the molar ratio of 3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 2- (4- aminophenyl) -5- aminobenzimidazole
For 1:(0.8~1.2), preferably 1:1.
Further, the organic solvent is selected from N-methyl pyrrolidones, dimethylformamide, dimethyl acetamide, two
One of first sulfoxide is a variety of；
And/or the in the mixed solvent, the volume fraction of organic solvent are 5%-50%.
The present invention also provides a kind of high-performance aromatic polymer fibers that the above method is prepared.
The present invention also provides a kind of composite material, the composite material is the high-performance virtue being in the above way prepared
Fragrant race's polymer fiber, epoxy resin are made from raw material.
Further, in the composite material, the mass fraction of high-performance aromatic polymer fiber is 40-60%, excellent
It is selected as 50%.
It is demonstrated experimentally that can be formed uniformly with metal ion using aromatic polymer fiber made from method of the invention
Polygamy bit architecture, excellent combination property, tensile property, compression performance, thermal stability are significantly increased.Utilize above-mentioned fragrance
Its epoxy resin composite material has further been made in race's polymer fiber, the present invention, and the interlaminar shear strength of the composite material is aobvious
It writes and improves, have a good application prospect.
In the present invention, 2- (4- aminophenyl) -5- aminobenzimidazole, that is, PABZ, p-phenylenediamine, that is, PDA, 3,3 ', 4,4 ' -
Bibenzene tetracarboxylic dianhydride, that is, BPDA, paraphthaloyl chloride, that is, TPC；Structure is as follows:
N-methyl pyrrolidones, that is, NMP, dimethylformamide, that is, DMF, dimethyl acetamide, that is, DMAC, diformazan in the present invention
Sulfoxide, that is, DMSO.
Dynamically continued through in the present invention refer to by polymer as-spun fibre be stretched across comprising transition metal ions (ratio
Such as Cu2+) solution tank device, to polymer as-spun fibre continuous processing.
As-spun fibre refers to the fiber of the polymer streams solidified forming in spinning field squeezed out from spinneret orifice in the present invention,
It is the fiber for having not gone through heat treatment；Finished fiber is the fiber that as-spun fibre obtains after Overheating Treatment.
Obviously, above content according to the present invention is not being departed from according to the ordinary technical knowledge and customary means of this field
Under the premise of the above-mentioned basic fundamental thought of the present invention, the modification, replacement or change of other diversified forms can also be made.
The specific embodiment of form by the following examples remakes further specifically above content of the invention
It is bright.But the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to example below.It is all to be based on above content of the present invention
The technology realized all belongs to the scope of the present invention.
Detailed description of the invention
Fig. 1 is the reaction process schematic diagram of aromatic polymer fiber prepared by the present invention.
Fig. 2 is the decaying In situ ATR-FTIR figure of aromatic polymer fiber prepared by the embodiment of the present invention 1.
Fig. 3 is the ultra-violet absorption spectrum that aromatic polymer fiber prepared by the embodiment of the present invention 1 is complexed by solution.
Specific embodiment
The raw materials used in the present invention, instrument are known product, are obtained by purchase commercial product.
The preparation of the aromatic polymer fiber of the present invention of embodiment 1 and its composite material
1, the preparation of aromatic polymer fiber of the present invention
First it polymerize to obtain aromatic polymer by monomer mole ratio TPC:PDA:PABZ=10:5:5, then passes through Wet-spinning
The aramid fiber as-spun fibre of the aromatic polymer is made in silk, and static immersing is including CuCl at 80 DEG C2(mass fraction 2%)
DMSO/ water mixed solution (DMSO volume fraction be 10%) in, after reacting 60mins, drying, then in 360 DEG C, nitrogen atmosphere
Lower progress no-station pole canopy static heat treatment is enclosed, finished fiber, i.e., aromatic polymer fiber of the invention are obtained.
2, the preparation of composite material of the present invention
Epoxy resin (mass fraction of fiber is 50%), preparation is added in the resulting aromatic polymer fiber of step 1
Obtain corresponding composite material.
The preparation of the aromatic polymer fiber of the present invention of embodiment 2 and its composite material
1, the preparation of aromatic polymer fiber of the present invention
First it polymerize to obtain aromatic polymer by monomer mole ratio TPC:PDA:PABZ=10:3:7, then passes through Wet-spinning
The aramid fiber as-spun fibre of the aromatic polymer is made in silk, and static immersing is including CuSO at 50 DEG C4(mass fraction
0.01%) in DMAc/ water mixed solution (DMAc volume fraction be 5%), after reacting 30mins, drying, then in 360 DEG C,
No-station pole canopy static heat treatment is carried out under nitrogen atmosphere, obtains finished fiber, i.e., aromatic polymer fiber of the invention.
2, the preparation of composite material of the present invention
Epoxy resin (mass fraction of fiber is 50%), preparation is added in the resulting aromatic polymer fiber of step 1
Obtain corresponding composite material.
The preparation of the aromatic polymer fiber of the present invention of embodiment 3 and its composite material
1, the preparation of aromatic polymer fiber of the present invention
First it polymerize to obtain aromatic polymer by monomer mole ratio TPC:PDA:PABZ=10:7:3, then passes through Wet-spinning
The aramid fiber as-spun fibre of the aromatic polymer is made in silk, and static immersing is including CuCl at 90 DEG C2(mass fraction
10%) in NMP/ water mixed solution (NMP volume fraction is 30%), after reacting 5mins, drying, then in 360 DEG C, nitrogen
No-station pole canopy static heat treatment is carried out under atmosphere, obtains finished fiber, i.e., aromatic polymer fiber of the invention.
2, the preparation of composite material of the present invention
Epoxy resin (mass fraction of fiber is 50%), preparation is added in the resulting aromatic polymer fiber of step 1
Obtain corresponding composite material.
The preparation of the aromatic polymer fiber of the present invention of embodiment 4 and its composite material
1, the preparation of aromatic polymer fiber of the present invention
First it polymerize to obtain aromatic polymer by monomer mole ratio TPC:PDA:PABZ=10:0:10, then passes through wet process
The aramid fiber as-spun fibre of the aromatic polymer is made in spinning, and static immersing is including CuCl at 70 DEG C2(mass fraction
1%) in DMAc/ water mixed solution (DMAc volume fraction is 20%), after reacting 300mins, drying, then in 360 DEG C, nitrogen
Atmosphere encloses lower progress no-station pole canopy static heat treatment, obtains finished fiber, i.e., aromatic polymer fiber of the invention.
2, the preparation of composite material of the present invention
Epoxy resin (mass fraction of fiber is 50%), preparation is added in the resulting aromatic polymer fiber of step 1
Obtain corresponding composite material.
The preparation of the aromatic polymer fiber of the present invention of embodiment 5 and its composite material
1, the preparation of aromatic polymer fiber of the present invention
First it polymerize to obtain aromatic polymer by monomer mole ratio TPC:PDA:PABZ=10:2:8, then passes through Wet-spinning
The aramid fiber as-spun fibre of the aromatic polymer is made in silk, and static immersing is including CuCl at 80 DEG C2(mass fraction 6%)
DMF/ water mixed solution (DMF volume fraction be 10%) in, after reacting 150mins, drying, then in 360 DEG C, nitrogen atmosphere
Lower progress no-station pole canopy static heat treatment, obtains finished fiber, i.e., aromatic polymer fiber of the invention.
2, the preparation of composite material of the present invention
Epoxy resin (mass fraction of fiber is 50%), preparation is added in the resulting aromatic polymer fiber of step 1
Obtain corresponding composite material.
The preparation of the aromatic polymer fiber of the present invention of embodiment 6 and its composite material
1, the preparation of aromatic polymer fiber of the present invention
First it polymerize to obtain aromatic polymer by monomer mole ratio TPC:PDA:PABZ=10:1:9, then passes through Wet-spinning
The aramid fiber as-spun fibre of the aromatic polymer is made in silk, and static immersing is including CuSO at 80 DEG C4(mass fraction
0.5%) in DMSO/ water mixed solution (DMSO volume fraction be 25%), after reacting 10mins, drying, then in 360 DEG C,
No-station pole canopy static heat treatment is carried out under nitrogen atmosphere, obtains finished fiber, i.e., aromatic polymer fiber of the invention.
2, the preparation of composite material of the present invention
Epoxy resin (mass fraction of fiber is 50%), preparation is added in the resulting aromatic polymer fiber of step 1
Obtain corresponding composite material.
The preparation of the aromatic polymer fiber of the present invention of embodiment 7 and its composite material
1, the preparation of aromatic polymer fiber of the present invention
First it polymerize to obtain aromatic polymer by monomer mole ratio TPC:PDA:PABZ=10:5:5, then passes through Wet-spinning
The aramid fiber as-spun fibre of the aromatic polymer is made in silk, and dynamic is by the inclusion of there is CuSO at 60 DEG C4(mass fraction 0.1%)
DMSO/ water mixed solution (DMSO volume fraction be 30%) in, after reacting 0.5mins, drying, then in 380 DEG C, nitrogen atmosphere
Hot-stretch containing tension is carried out under enclosing, and obtains finished fiber, i.e., aromatic polymer fiber of the invention (its reaction process schematic diagram
As shown in Figure 1).
2, the preparation of composite material of the present invention
Epoxy resin (mass fraction of fiber is 50%), preparation is added in the resulting aromatic polymer fiber of step 1
Obtain corresponding composite material.
The preparation of the aromatic polymer fiber of the present invention of embodiment 8 and its composite material
1, the preparation of aromatic polymer fiber of the present invention
First it polymerize to obtain aromatic polymer by monomer mole ratio TPC:PDA:PABZ=10:4:6, then passes through Wet-spinning
The aramid fiber as-spun fibre of the aromatic polymer is made in silk, and dynamic is by the inclusion of there is CuCl at 95 DEG C2(mass fraction 30%)
DMAc/ water mixed solution (DMAc volume fraction be 10%) in, after reacting 0.1mins, drying, then in 360 DEG C, nitrogen atmosphere
Lower progress no-station pole canopy static heat treatment is enclosed, finished fiber, i.e., aromatic polymer fiber of the invention are obtained.
2, the preparation of composite material of the present invention
Epoxy resin (mass fraction of fiber is 50%), preparation is added in the resulting aromatic polymer fiber of step 1
Obtain corresponding composite material.
The preparation of the aromatic polymer fiber of the present invention of embodiment 9 and its composite material
1, the preparation of aromatic polymer fiber of the present invention
First it polymerize to obtain aromatic polymer by monomer mole ratio TPC:PDA:PABZ=10:4:6, then passes through Wet-spinning
The aramid fiber as-spun fibre of the aromatic polymer is made in silk, and dynamic is by the inclusion of there is CuCl at 85 DEG C2(mass fraction 30%)
DMAc/ water mixed solution (DMAc volume fraction be 40%) in, after reacting 0.1mins, drying, then in 380 DEG C, nitrogen atmosphere
Hot-stretch containing tension is carried out under enclosing, and obtains finished fiber, i.e., aromatic polymer fiber of the invention.
2, the preparation of composite material of the present invention
Epoxy resin (mass fraction of fiber is 50%), preparation is added in the resulting aromatic polymer fiber of step 1
Obtain corresponding composite material.
The preparation of the aromatic polymer fiber of the present invention of embodiment 10 and its composite material
1, the preparation of aromatic polymer fiber of the present invention
First it polymerize to obtain aromatic polymer by monomer mole ratio TPC:PDA:PABZ=10:5:5, then passes through Wet-spinning
The aramid fiber as-spun fibre of the aromatic polymer is made in silk, and dynamic is by the inclusion of there is CuCl at 80 DEG C2(mass fraction 20%)
DMAc/ water mixed solution (DMAc volume fraction be 50%) in, after reacting 0.1mins, drying, then in 360 DEG C, nitrogen atmosphere
Lower progress no-station pole canopy static heat treatment is enclosed, finished fiber, i.e., aromatic polymer fiber of the invention are obtained.
2, the preparation of composite material of the present invention
Epoxy resin (mass fraction of fiber is 50%), preparation is added in the resulting aromatic polymer fiber of step 1
Obtain corresponding composite material.
The preparation of the aromatic polymer fiber of the present invention of embodiment 11 and its composite material
1, the preparation of aromatic polymer fiber of the present invention
First it polymerize to obtain aromatic polymer by monomer mole ratio BPDA:PABZ=1:1, is then made by wet spinning
The aramid fiber as-spun fibre of the aromatic polymer, dynamic is by the inclusion of there is CuSO at 70 DEG C4The DMAc/ of (mass fraction 8%)
In water mixed solution (DMAc volume fraction be 20%), after reacting 0.5mins, drying, then under 380 DEG C, nitrogen atmosphere into
Row hot-stretch containing tension, obtains finished fiber, i.e., aromatic polymer fiber of the invention.
2, the preparation of composite material of the present invention
Epoxy resin (mass fraction of fiber is 50%), preparation is added in the resulting aromatic polymer fiber of step 1
Obtain corresponding composite material.
The preparation of the aromatic polymer fiber of the present invention of embodiment 12 and its composite material
1, the preparation of aromatic polymer fiber of the present invention
First it polymerize to obtain aromatic polymer by monomer mole ratio BPDA:PABZ=1:1, is then made by wet spinning
The aramid fiber as-spun fibre of the aromatic polymer, dynamic is by the inclusion of there is CuSO at 85 DEG C4The DMF/ water of (mass fraction 2%) is mixed
In conjunction solution (DMF volume fraction is 10%), after reacting 0.8mins, then drying carries out nothing under 360 DEG C, nitrogen atmosphere
Power static heat treatment obtains finished fiber, i.e., aromatic polymer fiber of the invention.
2, the preparation of composite material of the present invention
Epoxy resin (mass fraction of fiber is 50%), preparation is added in the resulting aromatic polymer fiber of step 1
Obtain corresponding composite material.
The preparation of the aromatic polymer fiber of the present invention of embodiment 13 and its composite material
1, the preparation of aromatic polymer fiber of the present invention
First it polymerize to obtain aromatic polymer by monomer mole ratio BPDA:PABZ=1:1, is then made by wet spinning
The aramid fiber as-spun fibre of the aromatic polymer, dynamic is by the inclusion of there is CuCl at 60 DEG C2(mass fraction 0.1%)
In DMAc/ water mixed solution (DMAc volume fraction is 50%), after reacting 0.3mins, drying, then in 360 DEG C, nitrogen atmosphere
Lower progress no-station pole canopy static heat treatment, obtains finished fiber, i.e., aromatic polymer fiber of the invention.
2, the preparation of composite material of the present invention
Epoxy resin (mass fraction of fiber is 50%), preparation is added in the resulting aromatic polymer fiber of step 1
Obtain corresponding composite material.
The preparation of the aromatic polymer fiber of the present invention of embodiment 14 and its composite material
1, the preparation of aromatic polymer fiber of the present invention
First it polymerize to obtain aromatic polymer by monomer mole ratio BPDA:PABZ=1:1, is then made by wet spinning
The aramid fiber as-spun fibre of the aromatic polymer, it includes CuCl that static state, which is immersed in, at 60 DEG C2(mass fraction 6%)
In DMAc/ water mixed solution (DMAc volume fraction is 20%), after reacting 120mins, drying, then in 360 DEG C, nitrogen atmosphere
Lower progress no-station pole canopy static heat treatment, obtains finished fiber, i.e., aromatic polymer fiber of the invention.
2, the preparation of composite material of the present invention
Epoxy resin (mass fraction of fiber is 50%), preparation is added in the resulting aromatic polymer fiber of step 1
Obtain corresponding composite material.
The preparation of the aromatic polymer fiber of the present invention of embodiment 15 and its composite material
1, the preparation of aromatic polymer fiber of the present invention
First it polymerize to obtain aromatic polymer by monomer mole ratio BPDA:PABZ=1:1, is then made by wet spinning
The aramid fiber as-spun fibre of the aromatic polymer, it includes CuSO that static state, which is immersed in, at 50 DEG C4(mass fraction 0.1%)
In NMP/ water mixed solution (NMP volume fraction is 20%), after reacting 60mins, drying, then under 360 DEG C, nitrogen atmosphere
No-station pole canopy static heat treatment is carried out, finished fiber, i.e., aromatic polymer fiber of the invention are obtained.
2, the preparation of composite material of the present invention
Epoxy resin (mass fraction of fiber is 50%), preparation is added in the resulting aromatic polymer fiber of step 1
Obtain corresponding composite material.
The preparation of the aromatic polymer fiber of the present invention of embodiment 16 and its composite material
1, the preparation of aromatic polymer fiber of the present invention
First it polymerize to obtain aromatic polymer by monomer mole ratio BPDA:PABZ=1:1, is then made by wet spinning
The aramid fiber as-spun fibre of the aromatic polymer, it includes CuSO that static state, which is immersed in, at 90 DEG C4The NMP/ of (mass fraction 5%)
In water mixed solution (NMP volume fraction is 30%), after reacting 300mins, then drying carries out under 380 DEG C, nitrogen atmosphere
Hot-stretch containing tension obtains finished fiber, i.e., aromatic polymer fiber of the invention.
2, the preparation of composite material of the present invention
Epoxy resin (mass fraction of fiber is 50%), preparation is added in the resulting aromatic polymer fiber of step 1
Obtain corresponding composite material.
The following are the preparation methods of control sample.
Comparative example 1 compares the preparation of aromatic polymer fiber and its composite material
1, the preparation of aromatic polymer fiber is compared
It polymerize to obtain aromatic polymer (with gathering in embodiment 1 by monomer mole ratio TPC:PDA:PABZ=10:5:5
It is identical to close object), the aramid fiber as-spun fibre of the aromatic polymer is then made by wet spinning, then in 360 DEG C, nitrogen atmosphere
Lower progress no-station pole canopy static heat treatment is enclosed, finished fiber is obtained, is i.e. comparison aromatic polymer fiber is (without metal ion solution
Processing).
2, the preparation of comparative composite
Epoxy resin (mass fraction of fiber is 50%) is added in the resulting comparison aromatic polymer fiber of step 1,
Corresponding comparative composite is prepared.
Comparative example 2 compares the preparation of aromatic polymer fiber and its composite material
1, the preparation of aromatic polymer fiber is compared
It polymerize to obtain aromatic polymer (with the polymer phase in embodiment 15 by monomer mole ratio BPDA:PABZ=1:1
Together), the aramid fiber as-spun fibre of the aromatic polymer then is made by wet spinning, then under 360 DEG C, nitrogen atmosphere into
Row no-station pole canopy static heat treatment, obtains finished fiber, i.e. comparison aromatic polymer fiber (without metal ion solution processing).
2, the preparation of comparative composite
Epoxy resin (mass fraction of fiber is 50%) is added in the resulting comparison aromatic polymer fiber of step 1,
Corresponding comparative composite is prepared.
Comparative example 3 compares the preparation of aromatic polymer fiber and its composite material
1, the preparation of aromatic polymer fiber is compared
By the CuCl in embodiment 12Replace with FeCl3, it is prepared according to identical technique, specific as follows:
First it polymerize to obtain aromatic polymer by monomer mole ratio TPC:PDA:PABZ=10:5:5, then passes through Wet-spinning
The aramid fiber as-spun fibre of the aromatic polymer is made in silk, and static immersing is including FeCl at 80 DEG C3(mass fraction 2%)
DMSO/ water mixed solution (DMSO volume fraction be 10%) in, after reacting 60mins, drying, then in 360 DEG C, nitrogen atmosphere
Lower progress no-station pole canopy static heat treatment is enclosed, finished fiber is obtained, is i.e. comparison aromatic polymer fiber.
2, the preparation of comparative composite
Epoxy resin (mass fraction of fiber is 50%) is added in the resulting comparison aromatic polymer fiber of step 1,
Corresponding comparative composite is prepared.
Comparative example 4 compares the preparation of aromatic polymer fiber and its composite material
1, the preparation of aromatic polymer fiber is compared
First it polymerize to obtain aromatic polymer (in embodiment 1 by monomer mole ratio TPC:PDA:PABZ=10:5:5
Polymer phase is same), the aramid fiber as-spun fibre of the aromatic polymer is then made by wet spinning, then passes through as-spun fibre
Overheating Treatment obtains finished fiber, and then static immersing is including CuCl at 80 DEG C2The DMSO/ water of (mass fraction 2%)
In mixed solution (DMSO volume fraction is 10%), after reacting 60mins, then drying carries out nothing under 360 DEG C, nitrogen atmosphere
Tension static heat treatment is to get comparison aromatic polymer fiber (first finished product fiber, at metal ion solution
Reason).
2, the preparation of comparative composite
Epoxy resin (mass fraction of fiber is 50%) is added in the resulting comparison aromatic polymer fiber of step 1,
Corresponding comparative composite is prepared.
Comparative example 5 compares the preparation of aromatic polymer fiber and its composite material
1, the preparation of aromatic polymer fiber is compared
DMSO/ water mixed solution in embodiment 1 is replaced with into aqueous solution, is prepared according to identical technique, specific as follows:
First it polymerize to obtain aromatic polymer by monomer mole ratio TPC:PDA:PABZ=10:5:5, then passes through Wet-spinning
The aramid fiber as-spun fibre of the aromatic polymer is made in silk, and static immersing is including CuCl at 80 DEG C2(mass fraction 2%)
Aqueous solution in, react 60mins after, drying, then under 360 DEG C, nitrogen atmosphere carry out no-station pole canopy static heat treatment, obtain
Finished fiber, i.e. comparison aromatic polymer fiber.
2, the preparation of comparative composite
Epoxy resin (mass fraction of fiber is 50%) is added in the resulting comparison aromatic polymer fiber of step 1,
Corresponding comparative composite is prepared.
Comparative example 6 compares the preparation of aromatic polymer fiber and its composite material
1, the preparation of aromatic polymer fiber is compared
80 DEG C of temperature in embodiment 1 are replaced with 10 DEG C, are prepared according to identical technique, specific as follows:
First it polymerize to obtain aromatic polymer by monomer mole ratio TPC:PDA:PABZ=10:5:5, then passes through Wet-spinning
The aramid fiber as-spun fibre of the aromatic polymer is made in silk, and static immersing is including CuCl at 10 DEG C2(mass fraction 2%)
DMSO/ water mixed solution (DMSO volume fraction be 10%) in, after reacting 60mins, drying, then in 360 DEG C, nitrogen atmosphere
Lower progress no-station pole canopy static heat treatment is enclosed, finished fiber is obtained, is i.e. comparison aromatic polymer fiber.
2, the preparation of comparative composite
Epoxy resin (mass fraction of fiber is 50%) is added in the resulting comparison aromatic polymer fiber of step 1,
Corresponding comparative composite is prepared.
Beneficial effects of the present invention are proved below by way of experimental example.
Experimental example 1, structural characterization
1, decaying In situ ATR-FTIR (ATR-FTIR) test
Using 560 FTIR spectrometer of Nicolet (Thermo Electron) prepared by the embodiment of the present invention 1
Aromatic polymer fiber carry out decaying In situ ATR-FTIR test, as a result as shown in Figure 2, it can be seen that in 1492-
1495cm-1There is Ni metal in range2The absorption vibration peak of C=N, represents fibrous inside and introduces metal ion after coordination.
2, ultra-violet absorption spectrum is tested
The aromatic polymer fiber using UV-1 800PC spectrophotometer prepared by the embodiment of the present invention 1
After solution complexing, ultra-violet absorption spectrum test is carried out, as a result as shown in Figure 3, it can be seen that Cu occur at the peak of 435nm2+Cooperation
The absorption of object further proves that fibrous inside of the invention introduces metal ion.
The tensile strength test of experimental example 2, aromatic polymer fiber of the present invention
1, experimental method
The aromatic polymer being prepared using YG001A-1 filamentary electrons strength tester test 1-15 of the embodiment of the present invention
The tensile strength of fiber, the contrast sample with comparative example 1-6 preparation are control.
2, experimental result
It the results are shown in Table 1, it can be seen that the aromatic polymer fiber of high tensile has been prepared in the present invention, especially
It is the aromatic polyamide quasi polymer that embodiment 1-10 is prepared, tensile strength 4.1-4.4GPa.
The compressive strength test of experimental example 3, aromatic polymer fiber of the present invention
1, experimental method
The compressive strength for the aromatic polymer fiber that 1-15 of the embodiment of the present invention is prepared is tested using rebound method, with
The contrast sample of comparative example 1-6 preparation is control.
2, experimental result
It the results are shown in Table 1, it can be seen that the aromatic polymer fiber of high compression-strength has been prepared in the present invention, especially
It is
The aromatic polyamide quasi polymer that embodiment 1-15 is prepared, compressive strength are higher than any one comparison
Example.
Further comparing embodiment 1 and comparative example 1,3-6 and embodiment 15 and comparative example 2, it is found that the present invention
The compressive strength of the aromatic polymer fiber of preparation significantly improves, and only under specific process conditions of the invention, ability
The so high fiber of compression performance is made.
The glass transition temperature test of experimental example 4, aromatic polymer fiber of the present invention
1, experimental method
The aromatic polymer fiber being prepared using TA Q800 instrument test 1-15 of the embodiment of the present invention
Glass transition temperature, with comparative example 1-6 preparation contrast sample be control.
2, experimental result
It the results are shown in Table 1, it can be seen that the aromatic polymer that high glass-transition temperature has been prepared in the present invention is fine
Dimension, what especially embodiment 1-10 was prepared contains Cu2+The aramid fiber polymeric compound of coordination, glass transition temperature are higher than comparative example
1,3,4,5 and 6, illustrate only under process conditions of the invention specific, just can by coordination, be introduced into fiber molecule chain it
Between, the thermal stability for the fiber that the present invention is prepared can just improve, and further expand the use of fiber under the high temperature conditions
Range.
Further comparing embodiment 1 and comparative example 1,3-6 and embodiment 15 and comparative example 2, it is found that the present invention
The compressive strength of the aromatic polymer fiber of preparation significantly improves, and only under specific process conditions of the invention, ability
The so high fiber of thermal stability is made.
The interlaminar shear strength test of experimental example 5, composite material of the present invention
1, experimental method
The composite material being prepared using NOL ring shearing test according to GB1458-88 test 1-15 of the embodiment of the present invention
Interlaminar shear strength, with comparative example 1-6 preparation contrast sample be control.
2, experimental result
It the results are shown in Table 1, it can be seen that the composite material of high interlaminar shear strength has been prepared in the present invention, especially in fact
The composite material that a 1-10 is prepared is applied, interlaminar shear strength is higher than any one comparative example.
Further comparing embodiment 1 and comparative example 1,3-6 and embodiment 15 and comparative example 2, it is found that the present invention
The interlaminar shear strength of the composite material of preparation significantly improves, and could only be made under specific process conditions of the invention
The so high composite material of cutting performance.
In short, the virtue that the comprehensive performances such as tensile property, compression performance, thermal stability significantly improve has been prepared in the present invention
Fragrant race's polymer fiber and its composite material, wherein the group containing benzimidazole being prepared using TPC, PDA, PABZ as raw material
The compressive strength of Fypro be 659-809MPa, glass transition temperature is 268-290 DEG C, the Fypro and ring
The interlaminar shear strength for the composite material that oxygen resin is formed is 51-62MPa；Contain benzene using BPDA, PABZ as what raw material was prepared
And the compressive strength of the polyimide fiber of imidazole group is 954-1240MPa, glass transition temperature is 452-461 DEG C, should
The interlaminar shear strength for the composite material that polyimide fiber and epoxy resin are formed is 36-41MPa.
The performance test results of the aromatic polymer fiber prepared by the present invention of table 1 and its composite material, contrast sample
The uvioresistant aptitude tests of experimental example 6, composite material of the present invention
1, experimental method
After 240 hours ultraviolet light Continuous irradiations (3KW, 360nm), contrast test embodiment of the present invention 1-15 and comparative example
The mechanical property for the aromatic polymer fiber that 1-6 is prepared changes.
2, experimental result
It the results are shown in Table 1, it can be seen that aromatic polymer fiber produced by the present invention is in the ultraviolet light by 240 hours
After Continuous irradiation, tensile strength is only slightly reduced, substantially unchanged；And aromatic polymer fiber made from comparative example exists
After 240 hours ultraviolet light Continuous irradiations, being greatly reduced occurs in tensile strength.It proves only under the method for the present invention
The uvioresistant ability of aromatic polymer fiber obtained can just significantly improve.
This is because the method for the present invention introduces a large amount of transition metal ions on benzimidazole group, fiber occurs
Enhancement of Fluorescence, when by ultraviolet excitation, fiber can be more by the energy of absorption with the shape of fluorescent radiation transition
Formula is launched, and reduces fiber by molecule rotation/dissipation of vibrations energy ratio, to inhibit fiber by ultraviolet spoke
According to when its macromolecular chain rupture, it is possible to the effective ability for promoting fiber uvioresistant.
To sum up, the present invention provides a kind of aromatic polymer fiber and preparation method thereof, method system of the invention is utilized
The aromatic polymer fiber obtained can form uniform polygamy bit architecture, excellent combination property, draftability with metal ion
Energy, compression performance, thermal stability, uvioresistant ability are significantly increased.Using above-mentioned aromatic polymer fiber, the present invention is into one
Its epoxy resin composite material has been made in step, and the interlaminar shear strength of the composite material significantly improves, before having application well
Scape.
Claims (10)
1. a kind of preparation method of high-performance aromatic polymer fiber, it is characterised in that: the described method comprises the following steps: with
The as-spun fibre of aromatic polymer is raw material, is dipped in the solution containing transition metal ions, is reacted, drying, at heat
Reason to get.
2. preparation method according to claim 1, it is characterised in that: the transition metal ions is selected from Cu2+；
Preferably, the transition metal ions is by CuCl2、CuSO4One of or a variety of offers.
3. -2 described in any item preparation methods according to claim 1, it is characterised in that: the aromatic polymer is containing benzo
The aromatic polymer of glyoxaline structure, the preferably polyamide containing benzimidazole structure or the polyamides containing benzimidazole structure are sub-
Amine；
And/or the as-spun fibre is as made from wet spinning process；
And/or the solvent in the solution is selected from the mixed solvent of water and organic solvent；
And/or the mass fraction of transition metal ions is 0.01-30% in the solution；
The mode of the heat treatment are as follows: no-station pole canopy static heat treatment is carried out under 360 DEG C, nitrogen atmosphere, or, in 380 DEG C, nitrogen
Hot-stretch containing tension is carried out under atmosphere.
4. -2 described in any item preparation methods according to claim 1, it is characterised in that: the immersion mode is static immersing,
The reaction temperature is 50-90 DEG C, and the reaction time is 5-300min, it is preferable that the reaction temperature is 60-80 DEG C, institute
Stating the reaction time is 120-300min；
Or, the immersion mode is that dynamic continues through, the reaction temperature is 60-95 DEG C, and the reaction time is 0.1-
2min, it is preferable that the reaction temperature is 60-95 DEG C, and the reaction time is 0.1-0.3min.
5. preparation method according to claim 3, it is characterised in that: the aromatic polymer is by paraphenylene terephthalamide
Chlorine, 2- (4- aminophenyl) -5- aminobenzimidazole are what polymerizable raw material obtained；
Or, being obtained by paraphthaloyl chloride, 2- (4- aminophenyl) -5- aminobenzimidazole and p-phenylenediamine for polymerizable raw material
's；
Or, 3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 2- (4- aminophenyl) -5- aminobenzimidazole obtain by 3 for polymerizable raw material
's.
6. preparation method according to claim 5, it is characterised in that: the paraphthaloyl chloride: (p-phenylenediamine+2- (4-
Aminophenyl) -5- aminobenzimidazole) molar ratio be 1:1, wherein p-phenylenediamine and 2- (4- aminophenyl) -5- aminobenzene
And imidazoles) molar ratio be (0~7): (3~10)；
Or, described 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 2- (4- aminophenyl) -5- aminobenzimidazole molar ratio be 1:
(0.8~1.2), preferably 1:1.
7. preparation method according to claim 3, it is characterised in that: the organic solvent be selected from N-methyl pyrrolidones,
One of dimethylformamide, dimethyl acetamide, dimethyl sulfoxide are a variety of；
And/or the in the mixed solvent, the volume fraction of organic solvent are 5%-50%.
8. the high-performance aromatic polymer fiber that a kind of any one of claim 1-7 the method is prepared.
9. a kind of composite material, it is characterised in that: the composite material is prepared into any one of claim 1-7 the method
High-performance aromatic polymer fiber, the epoxy resin arrived is made from raw material.
10. composite material according to claim 9, it is characterised in that: in the composite material, the polymerization of high-performance aromatic series
The mass fraction of fibres be 40-60%, preferably 50%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110685157A (en) * | 2019-11-15 | 2020-01-14 | 哈尔滨工业大学 | Method for enhancing ultraviolet resistance of fiber by loading transition metal ions on fiber surface |
| CN114592344A (en) * | 2022-03-29 | 2022-06-07 | 武汉纺织大学 | Preparation method of high-strength high-toughness fiber material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49104943A (en) * | 1973-02-05 | 1974-10-04 | ||
| SU761623A1 (en) * | 1978-07-10 | 1980-09-07 | Vnii Sint Volokon | Polyamide thermal stabilization method |
| CN105102523A (en) * | 2013-04-09 | 2015-11-25 | 巴斯夫欧洲公司 | Stabilization of polyamide with copper-based metal organic frameworks |
| CN106758136A (en) * | 2016-12-29 | 2017-05-31 | 四川大学 | The aromatic polymer fiber of composite performance high containing benzimidazole and preparation method thereof |
-
2019
- 2019-04-30 CN CN201910364958.1A patent/CN110130095B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49104943A (en) * | 1973-02-05 | 1974-10-04 | ||
| SU761623A1 (en) * | 1978-07-10 | 1980-09-07 | Vnii Sint Volokon | Polyamide thermal stabilization method |
| CN105102523A (en) * | 2013-04-09 | 2015-11-25 | 巴斯夫欧洲公司 | Stabilization of polyamide with copper-based metal organic frameworks |
| CN106758136A (en) * | 2016-12-29 | 2017-05-31 | 四川大学 | The aromatic polymer fiber of composite performance high containing benzimidazole and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110685157A (en) * | 2019-11-15 | 2020-01-14 | 哈尔滨工业大学 | Method for enhancing ultraviolet resistance of fiber by loading transition metal ions on fiber surface |
| CN110685157B (en) * | 2019-11-15 | 2022-02-11 | 哈尔滨工业大学 | Method for enhancing ultraviolet resistance of fiber by loading transition metal ions on fiber surface |
| CN114592344A (en) * | 2022-03-29 | 2022-06-07 | 武汉纺织大学 | Preparation method of high-strength high-toughness fiber material |
| CN114592344B (en) * | 2022-03-29 | 2024-04-16 | 武汉纺织大学 | Preparation method of high-strength high-toughness fiber material |
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