CN108486867B - A kind of aromatic polymer fiber of high composite performance and preparation method thereof suitable for opposed polarity range matrix resin - Google Patents
A kind of aromatic polymer fiber of high composite performance and preparation method thereof suitable for opposed polarity range matrix resin Download PDFInfo
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- CN108486867B CN108486867B CN201810306994.8A CN201810306994A CN108486867B CN 108486867 B CN108486867 B CN 108486867B CN 201810306994 A CN201810306994 A CN 201810306994A CN 108486867 B CN108486867 B CN 108486867B
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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
- D06M11/77—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 silicon or compounds thereof
- D06M11/79—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 silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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- 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
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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- 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
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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- 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
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Abstract
The present invention relates to high-molecular compound preparation technical fields, in particular to a kind of aromatic polymer fiber of high composite performance and preparation method thereof suitable for opposed polarity range matrix resin.The described method includes: aromatic polymer fibre grafting is modified silica, then the active group that can be chemically bonded with the base resin is introduced by the Si-OH on the silica.Silica coarse structure is introduced into fiber surface by being grafted by the present invention, greatly improve the mechanical lock knot interaction between fiber surface and the resin of various opposed polarity ranges, then amino is re-introduced into using the Si-OH structure of silica, epoxy group, vinyl etc., and these groups can be formed at interface with the resin of opposed polarity range and are chemically bonded, fiber and resin are connected by strong chemical bond, therefore significantly improve the adhesive property of the various resins of polymer fiber and opposed polarity range.
Description
Technical field
The present invention relates to high-molecular compound preparation technical fields, are suitable for opposed polarity model in particular to one kind
Enclose the aromatic polymer fiber of high composite performance and preparation method thereof of matrix resin.
Background technique
Aromatic polymer fiber is a kind of high-strength and high-modulus high-performance fiber resistant to high temperature, and mostly important application is exactly
High-Performance Composite Materials Based on Resin as Matrix is prepared as reinforcement, suffers from and is widely applied in multiple military civil fields, including
With rubber is compound prepares tire and sebific duct, and epoxy resin, bimaleimide resin is compound prepares aircraft structure composite wood
Material, prepares high-end sports equipment with polypropylene composite materials.But aromatic polymer fiber does not have also as composite material reinforcement body
Have and play its excellent performance completely, this is because the overall performance of composite material depends not only on resin matrix and fiber
Performance, also and the interfacial adhesion of composite material is closely bound up.Aromatic polymer fiber possesses higher crystallinity and surface
Smooth, inertia is presented in surface, so it is poor with the adhesive property of various resins, so that the composite material prepared by it
It can be far below expection.
Generally, the adhesive property at fiber/polymer object interface is determined by three kinds of interactions.They are (1) machines
Tool lock knot；(2) polarities match；(3) it is chemically bonded.These interactions can be accordingly by increased fiber surface area, introducing
Van der Waals force/chemical bond etc. between electrostatic interaction and fiber and resin is introduced.Have largely about fibre at present
Dimension table face is modified to be reported to introduce these interactions, including soda acid processing, chemical oxidation, plasma and γ radiate and
Directly fluorination etc..However, most methods may be only available for a kind of resin matrix.This is because being glued with different resins matrix
It is different to tie the interaction needed, especially polarities match interacts.Different resin system polarity is different, they are needed
The fiber of opposed polarity carries out polarities match.For example, commonly using phosphoric acid processing to improve fiber/epoxy resin adhesive property
Fiber introduces polar carboxyl and hydroxyl on surface, is matched with improving fiber surface polarity with the higher epoxy resin of polarity
(Zhao J.Effect of surface treatment on the structure and properties of para-
aramid fibers by phosphoric acid[J].Fibers and Polymers,2013,14(1):59-64.).And
When carrying out compound tense with natural rubber, the above method is clearly inappropriate, this is because the polarity of rubber matrix itself is lower,
This requires the surfaces of aromatic polymer fiber should also have lower polarity, introduces carboxyl and hydroxyl further destroys instead
Polarities match in interface.Therefore, it is necessary to obtain it is a kind of can with the matrix resin of opposed polarity range have good interface
Aromatic polymer fiber of compatibility and preparation method thereof.
In view of this, the present invention is specifically proposed.
Summary of the invention
Primary and foremost purpose of the invention be in view of the deficiencies of the prior art, provide it is a kind of can be with opposed polarity range matrix resin
The preparation method of aromatic polymer fiber with good interface compatibility.
The secondary purpose of the present invention is to provide a kind of high composite performance aromatic polymer fibers prepared by the above method.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
The present invention relates to a kind of aromatic polymer of high composite performance suitable for opposed polarity range matrix resin fibres
The preparation method of dimension, comprising:
Aromatic polymer fibre grafting is modified into silica, then energy is introduced by the Si-OH on the silica
Enough active groups being chemically bonded with the base resin.
According to an aspect of the present invention, the invention further relates to the aromatic polymer fibres that method as described above is prepared
Dimension.
Since the benzimidazole group on aromatic polymer fiber is utilized as reaction site in the method for the present invention, carry out
Silica coarse structure is introduced into fiber surface by grafting, greatly improves the tree of fiber surface Yu various opposed polarity ranges
Mechanical lock knot interaction between rouge, is then re-introduced into amino, epoxy group, vinyl using the Si-OH structure of silica
Deng, and these groups can be formed at interface with the resin of opposed polarity range and are chemically bonded, it will by strong chemical bond
Fiber is connected with resin, therefore significantly improves the caking property of the various resins of polymer fiber and opposed polarity range
Can, obtain a kind of aromatic polymer fiber of high composite performance suitable for opposed polarity range matrix resin.
Since the method for the present invention is in the group (such as benzimidazole group) of aromatic polymer fiber surface chemical structure
The reaction of macromolecular side group is carried out, macromolecular main chain is completely retained, and relies on chemical oxidation treatment, plasma irradiation etc. with other
It is compared by the method for breaking to form active site of macromolecular main chain, does not destroy fiber bodies structure, can effectively solve to be modified
In journey the problem of fiber bodies mechanical properties decrease, the excellent results of the high composite performance of not damaged modification are realized.
Method and process provided by the invention is easy, and cost is relatively low, and modified effect is good, has stronger application prospect.
Specific embodiment
The present invention relates to a kind of aromatic polymer of high composite performance suitable for opposed polarity range matrix resin fibres
The preparation method of dimension, comprising:
Aromatic polymer fibre grafting is modified into silica, then energy is introduced by the Si-OH on the silica
Enough active groups being chemically bonded with the base resin.
Preferably, method as described above, the active group include at least one in vinyl, amino or epoxy group
Kind；It is furthermore preferred that the active group includes vinyl；And/or；At least one of amino or epoxy group；
Preferably, the active group is introduced in the form of the siloxanes containing active group；
It is furthermore preferred that the siloxanes containing active group includes methyl second when the active group is vinyl
Alkenyl cyclosiloxane, t etram-ethyltetravinylcyclotetrasiloxane, vinyl three (dimethyl siloxane) silane, vinyl front three
At least one of oxysilane；
It is furthermore preferred that when the active group is amino and/or epoxy group, the siloxanes packet containing active group
Include aminopropyl sealing end dimethyl silicone polymer, aminopropyl trimethoxysilane, aminopropyl triethoxysilane, three hydroxyl of 3- aminopropyl
Base silane, ethyoxyl aminopropyl dimethyl silicone polymer, γ-glycidyl ether oxygen propyl trimethoxy silicane, poly- (dimethyl
Siloxanes) end monoglycidyl ether, 3- glycidyl ether oxypropyltriethoxysilane, 3- glycydoxy first
At least one of base diethoxy silane.
Preferably, method as described above, the reaction condition for introducing the active group are that will be modified with silica
Described the containing of aromatic polymer fiber static immersing 0.1wt%~3wt% (more preferable 1 wt%~2wt% or 1.5wt%)
0.5h~2h (more preferable 1h~1.5h) is reacted in the siloxane solution of active group；Or；The virtue of silica will be modified with
Described the containing of fragrant race's polymer fiber and 1wt%~20wt% (more preferable 2wt%~15wt% or 5wt%~10wt%)
Active group siloxane solution dynamic successive reaction 0.1min~10min (min of more preferable 0.5min~6 or 1min~
5min or 2min~4min).
Preferably, method as described above, the aromatic polymer fiber are selected from the heteroaromatic polyamides containing benzimidazole
Amine fiber or polyimide fiber；
It is furthermore preferred that the heteroaromatic Fypro containing benzimidazole is by paraphthaloyl chloride, p-phenylenediamine and 5
(6)-amido -2- (4- aminocarbonyl phenyl) three kinds of monomers of benzimidazole are polymerizable raw material, spinning is prepared；It is furthermore preferred that used
In the chemical structure of monomer: paraphthaloyl chloride: p-phenylenediamine: 5 (6)-amido -2- (4- aminocarbonyl phenyl) benzimidazole rubs
You are than being 100:0~70:30~100；
It is furthermore preferred that the polyimide fiber is by 3,3', 4,4'- biphenyltetracarboxylic dianhydride and 5 (6)-amido -2- (4- amine
Base phenyl) three kinds of monomers of benzimidazole are that polymerizable raw material, spinning are prepared.
Preferably, the grafting and modifying method of method as described above, the silica includes:
1) is in the aromatic polymer surface grafting allyl；
2) 1) siloxane reactions of the reaction product in and the propyl containing mercapto are obtained the aromatic polymer containing siloxy by
Fiber；
3) hydrolyzes the aromatic polymer fiber containing siloxy in acid condition obtains surface containing silicone hydroxyl
Aromatic polymer fiber；
4) aromatic polymer fiber of the by the surface containing silicone hydroxyl and silicon dioxide gel solution reaction obtain surface
It is grafted with the aromatic polymer fiber of silica.
Since the method for the present invention has been firstly introduced into Si (OH) in grafting process3Structure turns monofunctional allyl
The Si-OH of trifunctional is turned to, Si-OH is then utilized again, participates in the condensation of silica, introduce coarse silica knot
The Si-OH content of structure, fiber surface greatly promotes, and is creatively significantly improved using the continuous stacked structure of silica
The grafting density of active function groups realizes the extension of aromatic polymer fiber inactive surfaces graft site.
Preferably, method as described above, step 1) specifically include:
By the aromatic polymer under the reaction system containing basic catalyst and phase transfer catalyst, with allyl
The ethanol solution of compound is reacted；
Preferably, the allyl compound in 3- bromopropene, chlorallylene, 3- iodopropylene, allyl alcohol at least
It is a kind of；
Preferably, the basic catalyst is hydroxide, hydride, the Organometallic of alkali metal or alkaline-earth metal
Close at least one of object；
Preferably, the phase transfer catalyst is selected from quaternary ammonium salt, tertiary amine, quaternary ammonium base, at least one of quaternary phosphonium salt；
Preferably, it is described reacted with the ethanol solution of allyl compound specially with the wt% alkene of 0.3wt%~3
Ethanol solution static immersing 6h~48h of compound, or it is dynamic with the ethanol solution of 3wt%~20wt% allyl compound
State successive reaction 1min~10min；
Preferably, it is described reacted with the ethanol solution of allyl compound specially with the wt% alkene of 0.5wt%~2
The ethanol solution static immersing 8h of compound~for 24 hours, or it is dynamic with the ethanol solution of 5wt%~15wt% allyl compound
State successive reaction 2min~7min.
Preferably, method as described above, step 2) specifically include:
By reaction product and the siloxanes of the propyl containing mercapto in 1) reacted under the promotion of radical initiator containing
The aromatic polymer fiber of siloxy；
Preferably, the siloxanes of the propyl containing mercapto is selected from gamma-mercaptopropyltriethoxysilane and/or mercapto propyl trimethoxy
Base silane；
Preferably, the siloxanes of the propyl containing mercapto is dissolved in ethyl alcohol；
It is furthermore preferred that the reaction temperature of the reaction is 45 DEG C~70 DEG C；More preferably 50 DEG C~65 DEG C or 55 DEG C~60
℃；
It is furthermore preferred that by reaction product and 1wt%~10wt% (wt% of more preferably 2wt%~9 in 1)；Or
4wt%~7wt%) the propyl containing mercapto siloxanes ethanol solution the wt% of 0.01wt%~0.1 (more preferably
0.03wt%~0.08wt%；Or 0.04wt%~0.06wt%) radical initiator promotion under static immersing 1h~6h (more
Preferably 2h~5h；Or 3h~4h)；Or；By in 1) reaction product and 5wt%~30wt% (more preferably 10wt%~
25wt%；Or the wt% of 15wt%~20) the propyl containing mercapto siloxanes ethanol solution 0.1wt%~1wt% (more preferably
For 0.3 wt%~0.7wt%；Or 0.4wt%~0.6wt%) radical initiator promotion under dynamic successive reaction 0.5min
~10min (more preferably 1min~8min；Or 3min~6min)；
Preferably, the radical initiator be selected from azodiisobutyronitrile, dibenzoyl peroxide, azobisisoheptonitrile,
Dilauroyl peroxide, the peroxidating trimethylacetic acid tert-butyl ester, di-isopropyl peroxydicarbonate, in dicyclohexyl peroxydicarbonate
It is at least one.
Preferably, method as described above, the pH of acid condition described in step 3) are 1~6, and more preferable pH is 2~5；
PH is 3~4；
Preferably, the acid condition is as produced by inorganic acid or organic acid soln；The inorganic acid includes sulfuric acid, salt
At least one of acid, phosphoric acid and nitric acid；The organic acid includes at least one of formic acid, acetic acid and oxalic acid；
Preferably, described to be hydrolyzed to static immersing hydrolysis 20min~60min；Or 0.5 min of dynamic continuous hydrolysis~
1min。
Preferably, method as described above, step 4) specifically include:
Aromatic polymer fiber static immersing by the surface containing silicone hydroxyl in 1wt%~50wt% (more preferably
5wt%~45wt%；Or 15wt%~35wt% or 20wt%~30wt%) 1h~for 24 hours is reacted in silicon dioxide gel solution
(more preferably 3h~20h；Or 5h~16h or 8h~12 are h)；Or；Aromatic polymer by the surface containing silicone hydroxyl is fine
Dimension static state and 10wt%~90wt% (more preferably 20wt%~80wt%；Or 40wt%~60wt% or 50wt%) dioxy
Dynamic successive reaction 0.1min~10min (more preferably 1min~8min in SiClx sol solution；Or 3min~6min).
According to an aspect of the present invention, the invention further relates to the aromatic polymer fibres that method as described above is prepared
Dimension.
The aromatic polymer fiber of high composite performance provided by the invention by above method preparation, modified fiber table
1000~1100cm of flushing outer display-1There is the peak of Si-O-Si key at place, in 900cm-1And 990cm-1There is the peak of vinyl at place,
1154cm-1There is the peak of amino at place, there is Si element energy spectral peak at the 103.6eV combination energy of x-ray photoelectron spectroscopy figure.Use the party
The interlaminar shear strength for the composite material that the heteroaromatic Fypro and epoxy resin of method preparation are formed is 56~64MPa, with
The interlaminar shear strength for the composite material that bimaleimide resin is formed is 40~44MPa, is formed with natural rubber compound
The interlaminar shear strength of material is 6~10MPa, relative to 117%, 166% and 43% has been respectively increased before modified；Use the party
The interlaminar shear strength for the composite material that the polyimide fiber containing benzimidazole and epoxy resin of method preparation are formed is 35~
39MPa, the interlaminar shear strength of the composite material formed with maleic anhydride resin are 26~29MPa, are formed with natural rubber
The interlaminar shear strength of composite material is 4.3~5.7MPa, relative to 45%, 67% and 37% has been respectively increased before modified.
Method and process step and condition provided by the present invention include following content:
(1) under room temperature, the aromatic polymer fiber static immersing of the group containing benzimidazole is being contained into basic catalyst
(the 0.1~1% of liquid quality fraction), phase transfer catalyst (the 0.1~1% of liquid quality fraction), allyl compound
In the ethanol solution of (the 0.3~3% of liquid quality fraction), 6h to 48h is reacted, or dynamic is continued through containing base catalysis
Agent (the 1~10% of liquid quality fraction), phase transfer catalyst (the 0.3~3% of liquid quality fraction), allyl compound
In the ethanol solution of (the 3~20% of liquid quality fraction), 1~10min is reacted；
(2) at 45~70 DEG C, the fiber static immersing of carbon-carbon double bond is containing radical initiator surface grafting
The ethyl alcohol of the siloxanes (the 1~10% of liquid quality fraction) of (the 0.01~0.1% of liquid quality fraction) and the propyl containing mercapto is molten
In liquid, 1h~6h is reacted, or dynamic is continued through containing radical initiator (the 0.1~1% of liquid quality fraction) and containing mercapto
In the ethanol solution of the siloxanes (the 5~30% of liquid quality fraction) of propyl, 0.5~10min is reacted；
(3) under room temperature, the acidity that the aromatic polymer fiber static immersing of siloxanes is 1~6 in pH is contained on surface
1~120min is hydrolyzed in aqueous solution, or dynamic continues through the acidic aqueous solution that pH is 1~6 and hydrolyzes 0.1~2min, then
Aromatic polymer fiber of the surface containing silicone hydroxyl can be obtained in drying；
(4) under room temperature, surface grafting there is into the fiber static immersing of silicone hydroxyl (solution matter in silicon dioxide gel solution
Measure the 1~50% of score), reaction 1h~for 24 hours, or dynamic is continued through containing silicon dioxide gel sol solution (solution quality
The 10~90% of score), react 0.1~10min；
(5) at room temperature, there is the fiber static immersing of silica (molten containing the siloxanes containing vinyl surface grafting
The 0.1~3% of liquid mass fraction) and the siloxanes (the 0.1~3% of liquid quality fraction) containing amino or epoxy group ethyl alcohol
In solution, 0.5h~2h is reacted, or dynamic is continued through containing vinyl (the 1~20% of liquid quality fraction) and containing amino
Or in the ethanol solution of (the 1~20% of liquid quality fraction) of epoxy group, 0.1~10min is reacted.Then vacuum drying is
The high activity aromatic polymer of amino/epoxy base and carbon-carbon double bond and silica coarse structure on surface grafting can be obtained
Fiber.
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
It can be with conventional products that are commercially available.
The compound that the abbreviation occurred in following embodiment and comparative examples represents are as follows:
Embodiment 1
It will first wrapped by Heterocyclic Aramid Fibre static immersing prepared by monomer mole ratio TPC:PDA:PABZ=10:5:5
It is the sodium hydroxide of liquid quality fraction 0.5% containing concentration, the ethyl alcohol of 0.3% four butyl bromation amine, 2% bromopropene is molten
In liquid, react 12h after dry, then static immersing include concentration be liquid quality fraction 0.03% two isobutyl of azo
Nitrile in the ethanol solution of 3% gamma-mercaptopropyltriethoxysilane, is dried, then static immersing is pH=5's after reacting 2h
Hydrolysis is dried after 25 minutes in aqueous hydrochloric acid solution, and the submergence of fiber static state is then put into the titanium dioxide that concentration is 20%
In silicon sol solution, reaction 60min drying, last middle static immersing is the second that liquid quality fraction is 2% including concentration
Alkenyl trimethoxy silane and 2% aminopropyl triethoxysilane ethanol solution, react 1h after dry.
Epoxy resin, bimaleimide resin, natural rubber is added in the Heterocyclic Aramid Fibre of the high composite performance of gained
Corresponding composite material is prepared, the correlated performance of gained composite material is seen attached list.
Embodiment 2
It will first wrapped by Heterocyclic Aramid Fibre static immersing prepared by monomer mole ratio TPC:PDA:PABZ=10:0:10
It is the sodium hydride of liquid quality fraction 0.1%, 0.3% tetrabutylammonium chloride, the ethanol solution of 3% iodopropylene containing concentration
In, react 6h after dry, then static immersing include concentration be liquid quality fraction 0.1% azodiisobutyronitrile,
In the ethanol solution of 10% gamma-mercaptopropyltriethoxysilane, dried after reacting 6h, then salt of the static immersing in pH=1
Hydrolysis is dried after 25 minutes in aqueous acid, and the submergence of fiber static state is then put into the silica that concentration is 50%
In sol solution, reaction 1h drying, last middle static immersing is the vinyl that liquid quality fraction is 0.1% including concentration
Three (dimethyl siloxane) silane and 0.1% aminopropyl sealing end dimethyl silicone polymer ethanol solution, react 2h after dry
It is dry.
Epoxy resin, bimaleimide resin, natural rubber is added in the Heterocyclic Aramid Fibre of the high composite performance of gained
Corresponding composite material is prepared, the correlated performance of gained composite material is seen attached list.
Embodiment 3
It will first wrapped by Heterocyclic Aramid Fibre static immersing prepared by monomer mole ratio TPC:PDA:PABZ=10:7:3
It is the butyl lithium of liquid quality fraction 1% containing concentration, the ethyl alcohol of 0.1% 4-butyl ammonium hydrogen sulfate, 0.3% chloropropene is molten
In liquid, react 48h after dry, then static immersing include concentration be liquid quality fraction 0.01% diphenyl peroxide first
Acyl in the ethanol solution of 1% gamma-mercaptopropyltriethoxysilane, is dried, then static immersing is pH=6's after reacting 1h
Hydrolysis is dried after 25 minutes in aqueous hydrochloric acid solution, and the submergence of fiber static state is then put into the titanium dioxide that concentration is 1%
In silicon sol solution, reaction is dried for 24 hours, and last middle static immersing is the ethylene that liquid quality fraction is 3% including concentration
(dimethyl siloxane) silane of base three and 3% aminopropyl trimethoxysilane ethanol solution, react 0.5h after drying be
It can.
Epoxy resin, bimaleimide resin, natural rubber is added in the Heterocyclic Aramid Fibre of the high composite performance of gained
Corresponding composite material is prepared, the correlated performance of gained composite material is seen attached list.
Embodiment 4
It will first wrapped by Heterocyclic Aramid Fibre static immersing prepared by monomer mole ratio TPC:PDA:PABZ=10:3:7
Containing concentration be liquid quality fraction 0.6% lithium diisopropylamine, 0.1% dodecyl trimethyl ammonium chloride, 0.3%
Allyl alcohol ethanol solution in, react 12h after dry, then static immersing include concentration be liquid quality fraction
0.03% dilauroyl peroxide in the ethanol solution of 1% γ-mercaptopropyl trimethoxysilane, is dried, then after reacting 6h
Static immersing hydrolysis in the aqueous hydrochloric acid solution of pH=6 is dried after 120 minutes, then puts the submergence of fiber static state
Enter in the silicon dioxide gel solution that concentration is 50%, reaction 2h drying, last middle static immersing is solution including concentration
Mass fraction is the ethanol solution of 2% vinyltrimethoxysilane and 2% 3- aminopropyl ortho-siliformic acid, after reacting 2h
Drying.
Epoxy resin, bimaleimide resin, natural rubber is added in the Heterocyclic Aramid Fibre of the high composite performance of gained
Corresponding composite material is prepared, the correlated performance of gained composite material is seen attached list.
Embodiment 5
It will first wrapped by Heterocyclic Aramid Fibre static immersing prepared by monomer mole ratio TPC:PDA:PABZ=10:5:5
Containing concentration be liquid quality fraction 0.2% sodium hydroxide, 0.1% hydroxide ethylamine, 1% bromopropene
In ethanol solution, react 8h after dry, then static immersing include concentration be liquid quality fraction 0.04% azo two
Different heptonitrile in the ethanol solution of 1% gamma-mercaptopropyltriethoxysilane, is dried, then static immersing is in pH=after reacting 2h
Hydrolysis is dried after 120 minutes in 3 aqueous hydrochloric acid solution, then by fiber static state submergence be put into concentration be 50% two
In silica sol solution, reaction 1min drying, it is last in static immersing including concentration be liquid quality fraction be 2%
Vinyltriethoxysilane and 2% ethyoxyl aminopropyl dimethyl silicone polymer ethanol solution, react 0.5h after dry
?.
Epoxy resin, bimaleimide resin, natural rubber is added in the Heterocyclic Aramid Fibre of the high composite performance of gained
Corresponding composite material is prepared, the correlated performance of gained composite material is seen attached list.
Embodiment 6
It will first wrapped by Heterocyclic Aramid Fibre static immersing prepared by monomer mole ratio TPC:PDA:PABZ=10:3:7
It is the hydrofining of liquid quality fraction 0.2%, 0.1% benzyltriethylammoinium chloride, the ethyl alcohol of 1% chloropropene containing concentration
In solution, react 8h after dry, then static immersing include concentration be liquid quality fraction 0.04% peroxidating uncle penta
Tert-butyl acrylate in the ethanol solution of 1% gamma-mercaptopropyltriethoxysilane, is dried, then static immersing is in pH after reacting 2h
Hydrolysis is dried after 120 minutes in=3 aqueous hydrochloric acid solution, and it is 50% that the submergence of fiber static state, which is then put into concentration,
Silicon dioxide gel solution in, reaction 1min drying, it is last in static immersing including concentration be that liquid quality fraction is
2% vinyltriethoxysilane and 2% γ-glycidyl ether oxygen propyl trimethoxy silicane ethanol solution, reaction
It is dried after 0.5h.
Epoxy resin, bimaleimide resin, natural rubber is added in the Heterocyclic Aramid Fibre of the high composite performance of gained
Corresponding composite material is prepared, the correlated performance of gained composite material is seen attached list.
Embodiment 7
It will first wrapped by Heterocyclic Aramid Fibre static immersing prepared by monomer mole ratio TPC:PDA:PABZ=10:4:6
It is the sodium hydride of liquid quality fraction 0.2%, 0.1% hydroxide ethyl ammonium, the second of 1% iodopropylene containing concentration
It in alcoholic solution, is dried after reacting 10h, then static immersing is including peroxidating two of the concentration for liquid quality fraction 0.05%
Diisopropyl carbonate in the ethanol solution of 1% gamma-mercaptopropyltriethoxysilane, is dried, then static immersing after reacting 4h
Hydrolysis is dried after sixty minutes in the aqueous hydrochloric acid solution of pH=5, and the submergence of fiber static state is then put into concentration and is
In 10% silicon dioxide gel solution, reaction 4min drying, it is last in static immersing including concentration for solution quality point
Number holds the ethanol solution of monoglycidyl ether for 1% vinyltriethoxysilane and 1% poly- (dimethyl siloxane),
It is dried after reacting 1h.
Epoxy resin, bimaleimide resin, natural rubber is added in the Heterocyclic Aramid Fibre of the high composite performance of gained
Corresponding composite material is prepared, the correlated performance of gained composite material is seen attached list.
Embodiment 8
It will first wrapped by Heterocyclic Aramid Fibre static immersing prepared by monomer mole ratio TPC:PDA:PABZ=10:2:8
It is the potassium hydroxide of liquid quality fraction 0.2% containing concentration, the ethyl alcohol of 0.1% tetramethylammonium hydroxide, 1% bromopropene is molten
In liquid, react 10h after dry, then static immersing include concentration be liquid quality fraction 0.05% dicetyl peroxydicarbonate
Diisopropyl ester in the ethanol solution of 1% gamma-mercaptopropyltriethoxysilane, is dried, then static immersing is in pH after reacting 4h
Hydrolysis is dried after sixty minutes in=5 aqueous hydrochloric acid solution, and it is 10% that the submergence of fiber static state, which is then put into concentration,
In silicon dioxide gel solution, reaction 4min drying, it is last in static immersing including concentration be liquid quality fraction be 1%
Vinyltriethoxysilane and 1% 3- glycidyl ether oxypropyltriethoxysilane ethanol solution, react 1h
It dries afterwards.
Epoxy resin, bimaleimide resin, natural rubber is added in the Heterocyclic Aramid Fibre of the high composite performance of gained
Corresponding composite material is prepared, the correlated performance of gained composite material is seen attached list.
Embodiment 9
It first will be by the continuous dipping of the dynamic of Heterocyclic Aramid Fibre prepared by monomer mole ratio TPC:PDA:PABZ=10:5:5
It is including butyl lithium that concentration is liquid quality fraction 3%, the ethyl alcohol of 1% four butyl bromation amine, 10% bromopropene is molten
It in liquid, is dried after reacting 10min, then dynamic is continuously immersed in the azo two for including concentration for liquid quality fraction 0.2%
Isobutyronitrile in the ethanol solution of 20% gamma-mercaptopropyltriethoxysilane, is dried after reacting 2min, then the continuous leaching of dynamic
Stain is dried after hydrolysis 0.5min in the aqueous hydrochloric acid solution of pH=1, is then put into the continuous dipping of fiber dynamic dense
Degree is in 50% silicon dioxide gel solution, reaction 5min drying, it is last in dynamic to be continuously immersed in include concentration be molten
Liquid mass fraction is 10% vinyltriethoxysilane and 10% 3- glycidyl ether oxypropyltriethoxysilane
Ethanol solution, react 5min after dry.
Epoxy resin, bimaleimide resin, natural rubber is added in the Heterocyclic Aramid Fibre of the high composite performance of gained
Corresponding composite material is prepared, the correlated performance of gained composite material is seen attached list.
Embodiment 10
It first will be by the continuous dipping of the dynamic of Heterocyclic Aramid Fibre prepared by monomer mole ratio TPC:PDA:PABZ=10:6:4
It is including sodium hydride of the concentration for liquid quality fraction 10%, 3% benzyltriethylammoinium chloride, the second of 20% iodopropylene
It in alcoholic solution, is dried after reacting 10min, then dynamic is continuously immersed in the azo for including concentration for liquid quality fraction 1%
Bis-isobutyronitrile in the ethanol solution of 30% gamma-mercaptopropyltriethoxysilane, is dried after reacting 10min, and then dynamic is continuous
It is immersed in the aqueous hydrochloric acid solution of pH=1 and is dried after hydrolysis 2min, is then put into the continuous dipping of fiber dynamic dense
Degree is in 90% silicon dioxide gel solution, reaction 10min drying, it is last in dynamic to be continuously immersed in include concentration be molten
Liquid mass fraction is 20% vinyltriethoxysilane and 20% 3- glycidyl ether oxypropyltriethoxysilane
Ethanol solution, react 10min after dry.
Epoxy resin, bimaleimide resin, natural rubber is added in the Heterocyclic Aramid Fibre of the high composite performance of gained
Corresponding composite material is prepared, the correlated performance of gained composite material is seen attached list.
Embodiment 11
It first will be by the continuous dipping of the dynamic of Heterocyclic Aramid Fibre prepared by monomer mole ratio TPC:PDA:PABZ=10:3:7
It is including sodium hydroxide of the concentration for liquid quality fraction 1%, 0.3% tetrabutylammonium bromide, the ethyl alcohol of 3% chloropropene
It in solution, is dried after reacting 1min, then dynamic is continuously immersed in the peroxidating two for including concentration for liquid quality fraction 1%
Benzoyl in the ethanol solution of 5% gamma-mercaptopropyltriethoxysilane, is dried after reacting 0.5min, then the continuous leaching of dynamic
Stain is dried after hydrolysis 0.1min in the aqueous hydrochloric acid solution of pH=1, is then put into the continuous dipping of fiber dynamic dense
It spends in the silicon dioxide gel solution for 10%, reaction 0.1min drying, it includes that concentration is that last middle dynamic, which is continuously immersed in,
Liquid quality fraction is 1% vinyltriethoxysilane and 1% 3- glycidyl ether oxypropyltriethoxysilane
Ethanol solution, react 0.1min after dry.
Epoxy resin, bimaleimide resin, natural rubber is added in the Heterocyclic Aramid Fibre of the high composite performance of gained
Corresponding composite material is prepared, the correlated performance of gained composite material is seen attached list.
Embodiment 12
It first will be by the continuous dipping of the dynamic of Heterocyclic Aramid Fibre prepared by monomer mole ratio TPC:PDA:PABZ=10:2:8
It is including sodium hydride of the concentration for liquid quality fraction 3%, 2% tetrabutylammonium iodide, the ethanol solution of 5% iodopropylene
In, it is dried after reacting 3min, then dynamic is continuously immersed in the diphenyl peroxide for including concentration for liquid quality fraction 0.5%
Formyl in the ethanol solution of 20% gamma-mercaptopropyltriethoxysilane, is dried after reacting 4min, then the continuous dipping of dynamic
It is dried after hydrolysis 0.5min in the aqueous hydrochloric acid solution of pH=4, the continuous dipping of fiber dynamic is then put into concentration
For in 60% silicon dioxide gel solution, reaction 2min drying, it is last in dynamic to be continuously immersed in include concentration be solution
Mass fraction is 15% vinyltriethoxysilane and 15% 3- glycidyl ether oxypropyltriethoxysilane
Ethanol solution is dried after reacting 2min.
Epoxy resin, bimaleimide resin, natural rubber is added in the Heterocyclic Aramid Fibre of the high composite performance of gained
Corresponding composite material is prepared, the correlated performance of gained composite material is seen attached list.
Embodiment 13
It first will be by the continuous dipping of the dynamic of Heterocyclic Aramid Fibre prepared by monomer mole ratio TPC:PDA:PABZ=10:1:9
It is including lithium diisopropylamine of the concentration for liquid quality fraction 5%, 1% hydroxide ethyl ammonium, 5% bromine
In the ethanol solution of propylene, react 3min after dry, then dynamic be continuously immersed in include concentration be liquid quality fraction
0.7% dibenzoyl peroxide in the ethanol solution of 10% γ-mercaptopropyl trimethoxysilane, is dried after reacting 6min,
Then dynamic is continuously immersed in the aqueous hydrochloric acid solution of pH=2 is dried after hydrolysis 1min, then connects fiber dynamic
Continuous impregnate is put into the silicon dioxide gel solution that concentration is 20%, and reaction 6min drying, last middle dynamic is continuously immersed in packet
It is γ-glycidyl ether oxygen propyl three of vinyltrimethoxysilane that liquid quality fraction is 12% and 12% containing concentration
The ethanol solution of methoxy silane is dried after reacting 5min.
Epoxy resin, bimaleimide resin, natural rubber is added in the Heterocyclic Aramid Fibre of the high composite performance of gained
Corresponding composite material is prepared, the correlated performance of gained composite material is seen attached list.
Embodiment 14
It first will be by the continuous dipping of the dynamic of Heterocyclic Aramid Fibre prepared by monomer mole ratio TPC:PDA:PABZ=10:0:10
It is including potassium hydroxide of the concentration for liquid quality fraction 4%, 2% 4-butyl ammonium hydrogen sulfate, the second of 10% allyl alcohol
It in alcoholic solution, is dried after reacting 5min, then dynamic is continuously immersed in the peroxide for including concentration for liquid quality fraction 0.7%
Change the trimethylacetic acid tert-butyl ester, in 10% γ-mercaptopropyl trimethoxysilane ethanol solution, dries after reacting 6min, then move
State is continuously immersed in the aqueous hydrochloric acid solution of pH=2 and is dried after hydrolysis 1min, then by the continuous dipping of fiber dynamic
It is put into the silicon dioxide gel solution that concentration is 20%, reaction 6min drying, it includes dense that last middle dynamic, which is continuously immersed in,
Degree is γ-glycidyl ether oxygen propyl trimethoxy of the vinyltrimethoxysilane that liquid quality fraction is 12% and 12%
The ethanol solution of base silane is dried after reacting 5min.
Epoxy resin, bimaleimide resin, natural rubber is added in the Heterocyclic Aramid Fibre of the high composite performance of gained
Corresponding composite material is prepared, the correlated performance of gained composite material is seen attached list.
Embodiment 15
It first will be by the continuous dipping of the dynamic of Heterocyclic Aramid Fibre prepared by monomer mole ratio TPC:PDA:PABZ=10:3:7
It is including sodium hydride that concentration is liquid quality fraction 1%, 2% pyridine, in the ethanol solution of 10% bromopropene, reaction
It is dried after 5min, it includes that the dicetyl peroxydicarbonate two that concentration is liquid quality fraction 0.4% is different that then dynamic, which is continuously immersed in,
Propyl ester in the ethanol solution of 20% gamma-mercaptopropyltriethoxysilane, is dried after reacting 7min, then the continuous dipping of dynamic
It is dried after hydrolysis 1min in the aqueous hydrochloric acid solution of pH=3, the continuous dipping of fiber dynamic, which is then put into concentration, is
In 30% silicon dioxide gel solution, reaction 4min drying, it is last in dynamic to be continuously immersed in include concentration be solution matter
Measuring score is 2% (dimethyl siloxane) silane of vinyl three and 2% ethyoxyl aminopropyl dimethyl silicone polymer
Ethanol solution is dried after reacting 3min.
Epoxy resin, bimaleimide resin, natural rubber is added in the Heterocyclic Aramid Fibre of the high composite performance of gained
Corresponding composite material is prepared, the correlated performance of gained composite material is seen attached list.
Embodiment 16
It will include first dense by polyimide fiber static immersing prepared by monomer mole ratio BPDA:PABZ=1:1
Degree is the potassium hydroxide of liquid quality fraction 1%, 0.3% tetrabutylammonium iodide, in the ethanol solution of 2% chloropropene, instead
It is dried after answering 12h, then static immersing is including azodiisobutyronitrile that concentration is liquid quality fraction 0.04%, and 1%
In the ethanol solution of gamma-mercaptopropyltriethoxysilane, dried after reacting 2h, then static immersing is water-soluble in the hydrochloric acid of pH=4
Hydrolysis is dried after sixty minutes in liquid, and it is molten that the submergence of fiber static state is then put into the silicon dioxide gel that concentration is 5%
In liquid, reaction 12h drying, last middle static immersing is the vinyl trimethoxy that liquid quality fraction is 2% including concentration
Base silane and 2% aminopropyl trimethoxysilane ethanol solution, react 1h after dry.
Epoxy resin, bimaleimide resin, natural rubber is added in the polyimide fiber of the high composite performance of gained
Corresponding composite material is prepared, the correlated performance of gained composite material is seen attached list.
Embodiment 17
It will include first dense by polyimide fiber static immersing prepared by monomer mole ratio BPDA:PABZ=1:1
Degree is the potassium hydroxide of liquid quality fraction 1%, 0.3% tetrabutylammonium iodide, in the ethanol solution of 2% chloropropene, instead
It is dried after answering 12h, then static immersing is including azodiisobutyronitrile that concentration is liquid quality fraction 0.04%, and 1%
In the ethanol solution of gamma-mercaptopropyltriethoxysilane, dried after reacting 2h, then static immersing is water-soluble in the hydrochloric acid of pH=4
Hydrolysis is dried after sixty minutes in liquid, and it is molten that the submergence of fiber static state is then put into the silicon dioxide gel that concentration is 5%
In liquid, reaction 12h drying, last middle static immersing is the vinyl trimethoxy that liquid quality fraction is 2% including concentration
Base silane and 2% aminopropyl trimethoxysilane ethanol solution, react 1h after dry.
Epoxy resin, bimaleimide resin, natural rubber is added in the polyimide fiber of the high composite performance of gained
Corresponding composite material is prepared, the correlated performance of gained composite material is seen attached list.
Embodiment 18
It will include first dense by polyimide fiber static immersing prepared by monomer mole ratio BPDA:PABZ=1:1
Degree is the sodium hydride of liquid quality fraction 0.1%, 0.3% benzyltriethylammoinium chloride, the ethanol solution of 1% allyl alcohol
In, react 4h after dry, then static immersing include concentration be liquid quality fraction 0.1% the tertiary fourth of peroxidating trimethylacetic acid
Ester in the ethanol solution of 3% γ-mercaptopropyl trimethoxysilane, is dried, then static immersing is pH=2's after reacting 1h
Hydrolysis is dried after 120 minutes in aqueous hydrochloric acid solution, and the submergence of fiber static state is then put into the dioxy that concentration is 10%
In SiClx sol solution, reaction 5min drying, last middle static immersing is the second that liquid quality fraction is 1% including concentration
Alkenyl triethoxysilane and 1% γ-glycidyl ether oxygen propyl trimethoxy silicane ethanol solution, react 0.5h after dry
It is dry.
Epoxy resin, bimaleimide resin, natural rubber is added in the polyimide fiber of the high composite performance of gained
Corresponding composite material is prepared, the correlated performance of gained composite material is seen attached list.
Embodiment 19
It first will be continuously immersed in by the dynamic of polyimide fiber prepared by monomer mole ratio BPDA:PABZ=1:1 and include
Having concentration is the potassium hydroxide of liquid quality fraction 1%, and 2% pyridine in the ethanol solution of 10% allyl alcohol, reacts 3min
After dry, it includes azobisisoheptonitrile that concentration is liquid quality fraction 0.2% that then dynamic, which is continuously immersed in, 20%
It in the ethanol solution of γ-mercaptopropyl trimethoxysilane, is dried after reacting 2min, then dynamic is continuously immersed in the salt of pH=2
It is dried after hydrolysis 2min in aqueous acid, the continuous dipping of fiber dynamic is then put into the titanium dioxide that concentration is 30%
In silicon sol solution, reaction 5min drying, it is last in dynamic to be continuously immersed in include concentration be liquid quality fraction be 3%
Vinyltrimethoxysilane and 3% γ-glycidyl ether oxygen propyl trimethoxy silicane ethanol solution, react 3min after
Drying.
Epoxy resin, bimaleimide resin, natural rubber is added in the polyimide fiber of the high composite performance of gained
Corresponding composite material is prepared, the correlated performance of gained composite material is seen attached list.
Embodiment 20
It first will be continuously immersed in by the dynamic of polyimide fiber prepared by monomer mole ratio BPDA:PABZ=1:1 and include
Having concentration is the sodium hydride of liquid quality fraction 10%, 4% benzyltriethylammoinium chloride, the ethanol solution of 20% bromopropene
In, it is dried after reacting 5min, then dynamic is continuously immersed in two isobutyl of azo for including concentration for liquid quality fraction 2%
Nitrile in the ethanol solution of 20% gamma-mercaptopropyltriethoxysilane, is dried after reacting 6min, and then dynamic is continuously immersed in
It is dried after hydrolysis 1min in the aqueous hydrochloric acid solution of pH=3, the continuous dipping of fiber dynamic, which is then put into concentration, is
In 30% silicon dioxide gel solution, reaction 2min drying, it is last in dynamic to be continuously immersed in include concentration be solution matter
The ethanol solution that score is 10% vinyltriethoxysilane and 10% ethyoxyl aminopropyl dimethyl silicone polymer is measured,
It is dried after reacting 2min.
Epoxy resin, bimaleimide resin, natural rubber is added in the polyimide fiber of the high composite performance of gained
Corresponding composite material is prepared, the correlated performance of gained composite material is seen attached list.
Comparative example 1
It will be prepared by monomer mole ratio TPC:PDA:PABZ=10:5:5 according to the same method of embodiment 1 and technique
To the Heterocyclic Aramid Fibre ontology without any surface treatment.
Epoxy resin, bismaleimide tree is added in the obtained Heterocyclic Aramid Fibre ontology without any surface treatment
Rouge, natural rubber prepare corresponding composite material, and the correlated performance of gained composite material is seen attached list.
Comparative example 2
It will be by monomer mole ratio TPC:PDA:PABZ=10:5:5 preparation according to the same method of embodiment 1 and technique
Heterocyclic Aramid Fibre carries out propenyl compounds grafting, then is grafted sulfydryl class silicone compounds.
Epoxy resin, bismaleimide is added in the Heterocyclic Aramid Fibre of obtained grafting sulfydryl class silicone compounds
Resin, natural rubber prepare corresponding composite material, and the correlated performance of gained composite material is seen attached list.
Comparative example 3
It will be by monomer mole ratio TPC:PDA:PABZ=10:5:5 preparation according to the same method of embodiment 1 and technique
Heterocyclic Aramid Fibre carries out grafted propylene based compound, then is grafted sulfydryl class silicone compounds, and last static state is immersed in dioxy
Reaction introduces silicon dioxide structure in SiClx sol solution.
Epoxy resin, bismaleimide is added in the Heterocyclic Aramid Fibre of obtained surface grafting silica coarse structure
Polyimide resin, natural rubber prepare corresponding composite material, and the correlated performance of gained composite material is seen attached list.
Comparative example 4
It is according to the same method of embodiment 1 and technique that the polyamides prepared by monomer mole ratio BPDA:PABZ=1:1 is sub-
Amine fiber carries out propenyl compounds grafting, then is grafted sulfydryl class silicone compounds.
Epoxy resin, bismaleimide is added in the polyimide fiber of obtained grafting sulfydryl class silicone compounds
Resin, natural rubber prepare corresponding composite material, and the correlated performance of gained composite material is seen attached list.
Comparative example 5
This comparative example is after being handled its surface aramid III fiber prepared by comparative example 1 with plasma, then
Epoxy resin, bimaleimide resin is added, natural rubber prepares corresponding composite material, the correlation of gained composite material
It can see attached list.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, but those skilled in the art should understand that: its
It is still possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features
It is equivalently replaced；And these are modified or replaceed, various embodiments of the present invention skill that it does not separate the essence of the corresponding technical solution
The range of art scheme.
Claims (21)
1. a kind of preparation method of the aromatic polymer fiber of the high composite performance suitable for opposed polarity range matrix resin,
It is characterised by comprising:
Aromatic polymer fibre grafting is modified into silica, then introducing by the Si-OH on the silica can be with
The active group that described matrix resin is chemically bonded；
The aromatic polymer fiber is selected from heteroaromatic Fypro or polyimide fiber containing benzimidazole；
The grafting and modifying method of the silica includes:
1) is grafted allyl in the aromatic polymer fiber surface；
2) 1) siloxane reactions of the reaction product in and the propyl containing mercapto are obtained the fibre of the aromatic polymer containing siloxy by
Dimension；
3) the aromatic polymer fiber containing siloxy is hydrolyzed the virtue containing silicone hydroxyl that obtains surface by acid condition
Fragrant race's polymer fiber；
4) aromatic polymer fiber of the by the surface containing silicone hydroxyl and silicon dioxide gel solution reaction obtain surface grafting
There is the aromatic polymer fiber of silica.
2. the method according to claim 1, wherein the active group includes vinyl, amino or epoxy
At least one of base；
The active group is introduced in the form of the siloxanes containing active group.
3. according to the method described in claim 2, it is characterized in that, when the active group be vinyl when, it is described to contain work
The siloxanes of property group includes methylvinylcyclosiloxane, t etram-ethyltetravinylcyclotetrasiloxane, three (dimethyl of vinyl
Siloxy group) silane, at least one of vinyltrimethoxysilane.
4. according to the method described in claim 2, it is characterized in that, when the active group be amino and/or epoxy group when, institute
Stating the siloxanes containing active group includes aminopropyl sealing end dimethyl silicone polymer, aminopropyl trimethoxysilane, aminopropyl
Triethoxysilane, 3- aminopropyl ortho-siliformic acid, ethyoxyl aminopropyl dimethyl silicone polymer, γ-glycidyl ether oxygen third
Base trimethoxy silane, poly- (dimethyl siloxane) hold monoglycidyl ether, 3- glycydoxy triethoxysilicane
At least one of alkane, 3- glycydoxy methyldiethoxysilane.
5. according to the method described in claim 2, will modify it is characterized in that, the reaction condition for introducing the active group is
There is the siloxanes containing active group of aromatic polymer fiber static immersing 0.1wt%~3wt% of silica
0.5h~2h is reacted in solution；Or；It will be modified with described in the aromatic polymer fiber and 1wt%~20wt% of silica
Siloxane solution dynamic successive reaction 0.1min~10min containing active group.
6. the method according to claim 1, wherein step 1) specifically includes:
By the aromatic polymer under the reaction system containing basic catalyst and phase transfer catalyst, with allyl chemical combination
The ethanol solution of object is reacted.
7. according to the method described in claim 6, it is characterized in that, the allyl compound is selected from 3- bromopropene, 3- chlorine third
At least one of alkene, 3- iodopropylene, allyl alcohol.
8. according to the method described in claim 6, it is characterized in that, the basic catalyst is alkali metal or alkaline-earth metal
At least one of hydroxide, hydride, metallo-organic compound.
9. according to the method described in claim 6, it is characterized in that, the phase transfer catalyst is selected from quaternary ammonium salt, tertiary amine, quaternary ammonium
Alkali, at least one of quaternary phosphonium salt.
10. according to the method described in claim 6, it is characterized in that, the ethanol solution with allyl compound carries out instead
Should be specially ethanol solution static immersing 6h~48h with 0.3wt%~3wt% allyl compound, or with 3wt%~
Ethanol solution dynamic successive reaction 1min~10min of 20wt% allyl compound.
11. the method according to claim 1, wherein step 2) specifically includes:
1) reaction product in is reacted to obtain containing silicon oxygen under the promotion of radical initiator with the siloxanes of the propyl containing mercapto
The aromatic polymer fiber of base.
12. according to the method for claim 11, which is characterized in that the siloxanes of the propyl containing mercapto is selected from γ-mercapto propyl
Triethoxysilane and/or mercaptopropyl trimethoxysilane.
13. according to the method for claim 11, which is characterized in that the siloxanes of the propyl containing mercapto is dissolved in ethyl alcohol.
14. according to the method for claim 11, which is characterized in that the reaction temperature of the reaction is 45 DEG C~70 DEG C.
15. according to the method for claim 11, which is characterized in that by the reaction product and 1wt%~10wt% in 1)
The ethanol solution of the siloxanes of the propyl containing mercapto under the promotion of 0.01wt%~0.1wt% radical initiator static immersing 1h~
6h；Or；By the ethanol solution of the siloxanes of the propyl containing mercapto of reaction product and 5wt%~30wt% in 1) 0.1wt%~
Dynamic successive reaction 0.5min~10min under the promotion of 1wt% radical initiator.
16. according to the method for claim 11, which is characterized in that the radical initiator be selected from azodiisobutyronitrile,
Dibenzoyl peroxide, azobisisoheptonitrile, dilauroyl peroxide, the peroxidating trimethylacetic acid tert-butyl ester, dicetyl peroxydicarbonate two are different
At least one of propyl ester, dicyclohexyl peroxydicarbonate.
17. the method according to claim 1, wherein the pH of acid condition described in step 3) is 1~6.
18. according to the method for claim 17, which is characterized in that the acid condition is by inorganic acid or organic acid soln institute
It generates；The inorganic acid includes at least one of sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid；The organic acid include formic acid, acetic acid and
At least one of oxalic acid.
19. according to the method for claim 17, which is characterized in that it is described be hydrolyzed to static immersing hydrolysis 20min~
60min；Or dynamic continuous hydrolysis 0.5min~1min.
20. the method according to claim 1, wherein step 4) specifically includes:
Aromatic polymer fiber static immersing by the surface containing silicone hydroxyl is molten in 1wt%~50wt% silicon dioxide gel
1h~for 24 hours is reacted in liquid；Or；Aromatic polymer fiber and 10wt%~90wt% titanium dioxide by the surface containing silicone hydroxyl
Dynamic successive reaction 0.1min~10min in silicon sol solution.
21. the aromatic polymer fiber that any one of claim 1~20 the method is prepared.
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