CN105821655B - A kind of aromatic polymer fiber of high composite performance and preparation method thereof - Google Patents
A kind of aromatic polymer fiber of high composite performance and preparation method thereof Download PDFInfo
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- CN105821655B CN105821655B CN201610319422.4A CN201610319422A CN105821655B CN 105821655 B CN105821655 B CN 105821655B CN 201610319422 A CN201610319422 A CN 201610319422A CN 105821655 B CN105821655 B CN 105821655B
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Abstract
High composite performance aromatic polymer fiber disclosed by the invention is that the aromatic polymer fiber for obtaining direct progress fluorinated surface processing is first handled with the silane coupler containing amino, then hydrolyzed with acidic aqueous solution, processing acquisition is carried out after with the silane coupler containing amino, epoxy radicals or pi-allyl again, the fiber surface contains and the reactive active group of matrix resin, its infrared 1100cm of display 1000‑1There is the peak of Si O Si keys at place, there is Si element energy spectral peaks at the 103.6eV combination energy of x-ray photoelectron energy spectrum diagram.Due to the inventive method on fiber surface chemical bonding the substantial amounts of active group such as amino, epoxide group or pi-allyl, itself and matrix resin or its curative systems can thus be connected by strong covalent bond, the cementability with matrix resin is greatly improved, the excellent results of the high composite performance of less fluorinated degree are realized.
Description
Technical field
The invention belongs to aromatic polymer fiber and its preparing technical field, and in particular to a kind of virtue of high composite performance
Fragrant race's polymer fiber and preparation method thereof.
Background technology
Aromatic polymer fiber belongs to the organic fiber of high strength and modulus, mainly including aromatic polyamide fibre
(the aramid fiber II and the aramid III fiber of copolymerization of such as homopolymerization) and polyparaphenylene's Benzo-dioxazole fiber (PBO), extensively should
For fields such as ballistic-resistant article, building materials, special type protection clothes and electronic equipments, its composite being made with resin has also been applied
The fields such as Aero-Space, defence and military.However, due to the highly crystalline highly oriented and smooth surface knot of aromatic polymer fiber
Structure, causes its composite performance with resin poor, so that the composite prepared by it can't fully meet Aero-Space
Deng the use requirement in field.It is then desired to improve aromatic polymer fiber and the composite property prepared by resin, such as
The mechanical strength of composite, interlaminar shear strength etc., these performances that improve composite are accomplished by improving aramid fiber
Surface-active, to improve the interaction force of aramid fiber surface and resin boundary surface.
Improve aromatic polymer fiber surface activity at present, improve its surface and matrix resin interfacial interaction power
Main method includes：Methods of chemical treatment such as corona method, plasma method, alkali or acid etc., but all there is this in these processing methods
Sample is clearly disadvantageous like that.Such as lived using the surface of the aromatic polymer fiber after corona method and plasma method processing
Property decay it is very fast, activity stability is inadequate；Polymer fiber macromolecular chain can be often set to break after being handled with chemical methodes such as alkali or acid
Chain, causes fiber bodies mechanical properties decrease.And the aromatic polymer fiber after the processing of these methods, it is compound to resin base
The enhancing effect of material is undesirable.Directly fluorination is the new technology of the Fiber strength of rising in recent years, and it is to utilize height
The fluorine gas of reactivity carries out surface modification to fiber as fluorination reagent, and its fluorinated polymeric material prepared is simply in table
Face forms nanometer layer, thus, do not influence polymeric material body mechanical property the advantages of low with cost.Once lead to before the present inventor
Cross aramid III fiber and pbo fiber that A the and CN 104911895A of CN 101798748 disclose direct fluorination treatment, make through
Aramid III fiber and pbo fiber surface after fluorination treatment take the groups such as polarity C-F and-COOH, are wherein fluorinated when using
The interlaminar shear strength of the composite prepared by aramid III fiber and epoxy resin afterwards is up to 47.3-55MPa, when using
Pbo fiber after being wherein fluorinated and the composite interlayer shear strength prepared by epoxy resin reach 30-45MPa.Although compared with
For untreated aramid III and pbo fiber, the composite property that after processing prepared by aramid III and pbo fiber has necessarily
Raising, but after fluorination the newly-increased chemical group of fiber surface and matrix resin mainly by way of Physical interaction come
The interfacial adhesion of fiber and resin is improved, compared to chemical bonding effect, Physical interaction undoubtedly can be weaker,
If reaching more preferable bonding interface effect, it is necessary to increase degree of fluorination.However, have document report (Solomun T,
Schimanski A,Sturm H,et al.Efficient formation of difluoramino
functionalities by direct fluorination of polyamides[J].Macromolecules,2005,
38(10):4231-4236.), under larger degree of fluorination, some groups of polymer fiber, such as amido link are easily in fluorination
During be largely broken, so as to cause mechanical properties decrease (Luo L, Wu P, Cheng Z, the et al.Direct of aramid fiber
fluorination of para-aramid fibers 1:Fluorination reaction process of PPTA
fiber[J].Journal of Fluorine Chemistry,2016,186:12-18.).Thus, how degree of fluorination compared with
In the case of low, the composite performance for keeping or further improving aromatic polymer fiber is pendulum in face of those skilled in the art
Research topic.
The content of the invention
The primary and foremost purpose of the present invention is that there is provided a kind of high composite performance aromatic polymer is fine in view of the shortcomings of the prior art
The preparation method of dimension.
The secondary objective of the present invention is to provide a kind of high composite performance aromatic polymer fiber prepared by the above method.
The preparation method for the high composite performance aromatic polymer fiber that the present invention is provided, the processing step and bar of this method
Part is as follows：
1) by aromatic polymer fiber, the method as disclosed in prior art directly carries out fluorinated surface processing and obtains surface
The aromatic polymer fiber of the group containing C-F；
2) under normal temperature, it is in mass percent concentration by the aromatic polymer fiber static immersing of surface group containing C-F
1~120min is reacted in the ethanol solution of 0.1~5% silane coupler containing amino, or dynamic continues through quality percentage
Specific concentration for 1~20% silane coupler containing amino ethanol solution and react 0.1~2min, then drying is to table
Contain the aromatic polymer fiber of siloxy in face；
3) under normal temperature, the aromatic polymer fiber static immersing of siloxy is contained into the acid water that pH is 1~6 in surface
1~120min is hydrolyzed in solution, or dynamic continues through the acidic aqueous solution that pH is 1~6 and hydrolyzes 0.1~2min, then dries
It is dry to can obtain aromatic polymer fiber of the surface containing silicone hydroxyl；
4) under normal temperature, it is in mass percent concentration by aromatic polymer fiber static immersing of the surface containing silicone hydroxyl
1~120min is reacted in the ethanol solution of 0.1~5% silane coupler containing amino, epoxy radicals or pi-allyl, or dynamic is continuously
The ethanol solution for 1~20% silane coupler containing amino, epoxy radicals or pi-allyl and reaction by mass percent concentration
0.1~2min, then aromatic polymer fiber of the drying to high composite performance.
1) aromatic polymer fiber used in step is Fanglun 1414's (virtue to above method the
Synthetic fibre II), any of heteroaromatic Fypro (aramid III) or polyparaphenylene's Benzo-dioxazole fiber (pbo fiber), its
In used polyparaphenylene's Benzo-dioxazole fiber be in poly by 4,6- diamino resorcin hydrochlorates and terephthalic acid (TPA)
The heated polymerization of phosphoric acid solvent, spinning are prepared from, and monomer chemistries structure is as follows：
The mol ratio of 4,6- diamino resorcin hydrochlorates and terephthalic acid (TPA) is 1:1.Poly- paraphenylene terephthalamide used
P-phenylenediamine fiber (aramid fiber II) is by two kinds of raw material monomers of paraphthaloyl chloride and p-phenylenediamine polymerize, spinning is prepared
's；Heteroaromatic Fypro (aramid III) is by paraphthaloyl chloride, p-phenylenediamine and 5 (6)-amido -2- (4- amido benzene
Base) three kinds of monomers of benzimidazole are that polymerizable raw material, spinning are prepared from.The chemical constitution of monomer used is as follows：
The mol ratio of paraphthaloyl chloride and p-phenylenediamine is 1 in wherein aramid fiber II:1；In aramid III, paraphenylene terephthalamide
Chlorine：P-phenylenediamine：5 (6)-amido -2- (4- aminocarbonyl phenyls) benzimidazole ratio is 100:0~70:30~100.
The prior art of the direct carry out fluorinated surface processing 1) described in step of above method be by the present inventor it
What the method in preceding disclosed CN 101798748A and CN 104911895A was handled, wherein fluorine gas partial pressure preferably 0.5~
5kPa, nitrogen partial pressure preferably 5~60kPa, and nitrogen partial pressure is at least 10 times of fluorination partial pressure.
Above method the 2) in step the ethanol solution of the silane coupler containing amino used in static immersing quality hundred
Divide specific concentration preferably 0.8~2%, soak time preferably 20~60min；Dynamic continuous processing is used to contain the silane coupled of amino
The mass percent concentration of the ethanol solution of agent preferably 4~10%, processing time preferably 0.5~1min.
The pH preferably 3~5 of the acidic aqueous solution 3) described in step of above method, static immersing hydrolysis time preferably 20
~60min；Dynamic continuous hydrolysis time preferably 0.5~1min.
Above method the 4) in step the silane coupler containing amino, epoxy radicals or pi-allyl used in static immersing ethanol
The mass percent concentration of solution preferably 0.8~2%, soak time preferably 20~60min；Dynamic continuous processing is used to contain ammonia
The mass percent concentration of the ethanol solution of the silane coupler of base, epoxy radicals or pi-allyl preferably 4~10%, processing time is excellent
Select 0.5~1min.
The silane coupler containing amino used is (3- aminopropyls) dimethylethoxysilane, (3- in above method
Aminopropyl) methyldiethoxysilane, (3- aminopropyls) triethoxysilane and (3- aminopropyls) trimethoxy silane
At least one of.
Acidic aqueous solution used is that inorganic acid or organic acid are formulated in above method, inorganic acid preferably sulfuric acid, salt
At least one of acid, phosphoric acid and nitric acid；At least one of the preferred formic acid of organic acid, acetic acid and oxalic acid.
The silane coupler containing amino, epoxy radicals or pi-allyl used is (3- aminopropyls) dimethyl in above method
Ethoxysilane, (3- aminopropyls) methyldiethoxysilane, (3- aminopropyls) triethoxysilane, (3- aminopropyls)
Trimethoxy silane, 3- glycidyl ether oxygen propyl trimethoxy silicanes, 3- glycidoxypropyltrietandysilane andysilanes, 3-
Appointing in glycydoxy methyl diethoxy silicon, vinyltrimethoxy silane or VTES
It is a kind of.
The aromatic polymer fiber for the high composite performance prepared by the above method that the present invention is provided, the fiber surface contains
Have and the reactive active group of matrix resin, its infrared display 1000-1100cm-1There is the peak of Si-O-Si keys at place, in X-ray
The 103.6eV of photoelectron spectroscopy figure, which is combined at energy, Si element energy spectral peaks, with the PPTA wherein prepared
The interlaminar shear strength of fiber (aramid fiber II) and the composite of epoxy resin formation is 38-45MPa, and impregnation silk intensity is 4.0-
4.5GPa；The interlayer of the composite formed with the heteroaromatic Fypro (aramid III) wherein prepared with epoxy resin is cut
Shearing stress is 52-60MPa, and impregnation silk intensity is 5.4-6.0GPa；With the polyparaphenylene's Benzo-dioxazole fiber wherein prepared
The interlaminar shear strength of (pbo fiber) and the composite of maleic anhydride resin formation is 36-48MPa, and impregnation silk intensity is
5.2-5.8GPa。
The present invention compared with prior art, has the advantages that：
1st, because the inventive method can not react merely with band amino silicane coupling agent with C-F keys and will contain Si-O groups
Be connected on the aromatic polymer fiber of surface group containing C-F, and can obtain Si-OH's by the hydrolysis of Si-O keys
Si-OH is creatively incorporated into aromatic polymer fiber surface by mode, and contains amino, epoxy radicals or allyl by adding again
The silane coupler of base continues to react with Si-OH, has been allowed on fiber surface chemical bonding substantial amounts of active group, such as ammonia
Base, epoxide group and pi-allyl etc., and these groups effectively can chemically react with matrix resin or its curative systems,
And can be connected aromatic polymer fiberoptic fiber with matrix resin or its curative systems by strong covalent bond
Come, thus the cementability of aromatic polymer fiber and matrix resin can be increased substantially, obtain a kind of high composite performance
Aromatic polymer fiber.
2nd, because the inventive method can be carried out in the chemical group that aromatic polymer fiber surface is increased newly with matrix resin
Chemical reaction, forms strong covalent bond and has been connected aromatic polymer fiber with matrix resin or its curative systems
Come, thus the bonding interface effect not only with matrix resin or its curative systems is good, and aromatic series polymerization need not be increased
The degree of fluorination of fibres, is improved and matrix resin or its solidification with fully relying on the direct fluorinated surface processing method of reinforcing
The interfacial adhesion of agent system is compared, and the fluorine gas consumption of fiber fluorination treatment is small, can be suppressed because of big the brought fibre of degree of fluorination
The adverse effect of body mechanical properties decrease is tieed up, the excellent results of the high composite performance of less fluorinated degree are realized.
2nd, because the present invention first passes through the aromatic polymer fiber that directly fluorination obtains surface group containing C-F, recycle
C-F keys will contain Si-O group chemicals with the reaction with amino silicane coupling agent and be connected to fiber surface, then pass through the water of Si-O keys
Solution can obtain Si-OH.
3rd, by the raw material chemical reactivity height that the method that the present invention is provided is used, it can also pass through in addition and control to prepare
During fluorine gas pressure, hydrolysis time and pH control obtained Si-OH content, you can pass through containing for Si-OH
Measure to control the content of the active group with resin or the reaction of its curing agent, thus the not only high conversion rate of each step, and can
Realize the controllability of reaction.
4th, the method that the present invention is provided is simple for process, and its cost is relatively low, with stronger application prospect.
Brief description of the drawings
Fig. 1 prepares the course of reaction schematic diagram of high composite performance aramid III fiber for the present invention.
Fig. 2 is the attenuated total reflectance infrared spectrogram (ATR- of the aramid III fiber obtained by the embodiment of the present invention 1
FTIR), wave-number range is 1000~1100cm in figure-1It is Si-O-Si absorption vibration peak.
Fig. 3 is the aramid III fiber x-ray photoelectron energy spectrum diagram (XPS) after the processing obtained by the embodiment of the present invention 1,
103.6eV, which is combined, in figure Si element energy spectral peaks at energy, 698eV combines the energy spectral peak for having unreacted F elements at energy.
Embodiment
Embodiment is given below so that the invention will be further described.It is necessarily pointed out that following examples can not
Be interpreted as limiting the scope of the invention, if the person skilled in the art in the field according to the invention described above content to this hair
It is bright to make some nonessential modifications and adaptations, still fall within the scope of the present invention.
In addition, what deserves to be explained is；1) the fluorination temperature of direct fluorinated aromatic polymers fiber is equal in following examples
For 30 DEG C, 10 minutes time is fluorinated during static state fluorination, the time that is fluorinated during dynamic continuous fluorination is 2 minutes.2) in following examples
The concentration of the ethanol solution of silane coupler used is mass percent concentration；3) it is used for Compound Material Engineering after its processing
The enhancing effect of performance is the dependence test carried out using epoxy-resin systems or maleic anhydride as matrix resin, wherein composite wood
The mass fraction of fiber is 50% in material.The method that the interlaminar shear strength of composite uses NOL rings, test result is shown in
Subordinate list.The tensile strength of impregnation silk is tested according to GBT3362-2005, and test result is seen attached list.Polymer fiber sheet
The tensile strength of body is to use Britain Instron4302 type strength testers, according to ASTM D 885-2007 method, according to fixture
Spacing 215mm, fixture translational speed 25mm/min, simple tension test, test result is seen attached list.
Embodiment 1
First will be by monomer mole ratio TPC:PDA:PABZ=10:5:Aramid III fiber prepared by 5 is disclosed with prior art
Method fluorination partial pressure be 1kPa, nitrogen partial pressure be 10kPa under directly progress fluorination treatment, it is then that the fiber after fluorination is quiet
State is immersed in reaction in the ethanol solution of (3- aminopropyls) triethoxysilane that concentration is 2% and dried after 30 minutes, then
Static immersing hydrolysis in pH=4 aqueous hydrochloric acid solution is dried after 25 minutes, and it is 2% that fiber finally is put into concentration
(3- aminopropyls) triethoxysilane ethanol solution in immersion reaction 30 minutes after dry.
The aramid III fiber of the high composite performance of gained is added into epoxy resin-base and prepares corresponding composite, gained
The correlated performance of composite is seen attached list.
Embodiment 2
First will be by monomer mole ratio TPC:PDA:PABZ=10:5:Aramid III fiber prepared by 5 is disclosed with prior art
Method fluorination partial pressure be 0.5kPa, nitrogen partial pressure be 5kPa under directly progress fluorination treatment, then by the fiber after fluorination
Static immersing reaction in ethanol solution of the concentration for 2% (3- aminopropyls) triethoxysilane is dried after 30 minutes, is connect
Static immersing hydrolysis in pH=4 aqueous hydrochloric acid solution to be dried after 30 minutes, fiber finally is put into concentration is
Immersion reaction is dried after 30 minutes in the ethanol solution of 3% (3- aminopropyls) triethoxysilane.
The aramid III fiber of the high composite performance of gained is added into epoxy resin-base and prepares corresponding composite, gained
The correlated performance of composite is seen attached list.
Embodiment 3
First will be by monomer mole ratio TPC:PDA:PABZ=10:5:Aramid III fiber prepared by 5 is disclosed with prior art
Method fluorination partial pressure be 1.5kPa, nitrogen partial pressure be 15kPa under directly progress fluorination treatment, then by the fiber after fluorination
Static immersing reaction in ethanol solution of the concentration for 1% (3- aminopropyls) trimethoxy silane is dried after 20 minutes, is connect
Static immersing hydrolysis in pH=5 aqueous sulfuric acid to be dried after 20 minutes, fiber finally is put into concentration is
Immersion reaction is dried after 40 minutes in the ethanol solution of 2% 3- glycidyl ether oxygen propyl trimethoxy silicanes.
The aramid III fiber of the high composite performance of gained is added into epoxy resin-base and prepares corresponding composite, gained
The correlated performance of composite is seen attached list.
Embodiment 4
First will be by monomer mole ratio TPC:PDA:PABZ=10:4:Aramid III fiber prepared by 6 is disclosed with prior art
Method fluorination partial pressure be 1.5kPa, nitrogen partial pressure be 15kPa under directly progress fluorination treatment, then by the fiber after fluorination
Static immersing reaction in ethanol solution of the concentration for 5% (3- aminopropyls) dimethylethoxysilane is dried after 10 minutes
Dry, then static immersing hydrolysis in pH=3 aqueous solution of nitric acid is dried after 60 minutes, is finally put into fiber dense
Immersion reaction in the ethanol solution for 0.8% 3- glycydoxy methyldiethoxysilanes is spent to dry after 20 minutes
It is dry.
The aramid III fiber of the high composite performance of gained is added into epoxy resin-base and prepares corresponding composite, gained
The correlated performance of composite is seen attached list.
Embodiment 5
First will be by monomer mole ratio TPC:PDA:PABZ=10:7:Aramid III fiber prepared by 3 is disclosed with prior art
Method fluorination partial pressure be 1kPa, nitrogen partial pressure be 10kPa under directly progress fluorination treatment, it is then that the fiber after fluorination is quiet
State is immersed in reaction in the ethanol solution of (3- aminopropyls) methyldiethoxysilane that concentration is 0.5% and dried after 100 minutes
Dry, then static immersing hydrolysis in pH=1 phosphate aqueous solution is dried after 1 minute, is finally put into fiber dense
Immersion reaction in the ethanol solution for 0.1% (3- aminopropyls) trimethoxy silane is spent to dry after 120 minutes.
The aramid III fiber of the high composite performance of gained is added into epoxy resin-base and prepares corresponding composite, gained
The correlated performance of composite is seen attached list.
Embodiment 6
First will be by monomer mole ratio TPC:PDA:PABZ=10:0:Aramid III fiber prepared by 10 is public with prior art
The method opened is 3kPa in fluorination partial pressure, and nitrogen partial pressure is directly carries out fluorination treatment under 40kPa, then by the fiber after fluorination
Static immersing is in (3- aminopropyls) trimethoxy silane and (3- aminopropyls) methyldiethoxysilane that concentration is 0.1%
Ethanol solution in reaction dry after 120 minutes, then static immersing 100 points of hydrolysis in pH=6 aqueous formic acid
Dried after clock, fiber is finally put into the ethanol solution of (3- aminopropyls) dimethylethoxysilane that concentration is 1%
Middle immersion reaction is dried after 90 minutes.
The aramid III fiber of the high composite performance of gained is added into epoxy resin-base and prepares corresponding composite, gained
The correlated performance of composite is seen attached list.
Embodiment 7
First will be by monomer mole ratio TPC:PDA=1:Method disclosed in aramid fiber II fiber prior arts prepared by 1 exists
Fluorination partial pressure is 1.5kPa, and nitrogen partial pressure is directly carries out fluorination treatment under 15kPa, then by the fiber static immersing after fluorination
Reaction is dried after 60 minutes in ethanol solution of the concentration for 0.8% (3- aminopropyls) trimethoxy silane, then static
It is immersed in hydrolysis in pH=4 acetic acid aqueous solution to be dried after 120 minutes, it is 0.5% that fiber finally is put into concentration
(3- aminopropyls) trimethoxy silane ethanol solution in immersion reaction 10 minutes after dry.
The aramid fiber II fibers of the high composite performance of gained are added into epoxy resin-base and prepare corresponding composite, gained is multiple
The correlated performance of condensation material is seen attached list.
Embodiment 8
First will be by monomer mole ratio TPC:PDA=1:Method disclosed in aramid fiber II fiber prior arts prepared by 1 exists
Fluorination partial pressure is 2kPa, and then nitrogen partial pressure exists the fiber static immersing after fluorination directly to carry out fluorination treatment under 20kPa
Concentration is reaction in 4% (3- aminopropyls) triethoxysilane and the ethanol solution of (3- aminopropyls) trimethoxy silane
Dried after 1 minute, then static immersing hydrolysis in pH=2 hydrochloric acid and sulfuric acid mixed aqueous solution is dried after 10 minutes
It is dry, fiber is finally put into immersion reaction 3 in the ethanol solution of (3- aminopropyls) methyldiethoxysilane that concentration is 5%
Dried after minute.
The aramid fiber II fibers of the high composite performance of gained are added into epoxy resin-base and prepare corresponding composite, gained is multiple
The correlated performance of condensation material is seen attached list.
Embodiment 9
First will be by monomer mole ratio TPC:PDA=1:Method disclosed in aramid fiber II fiber prior arts prepared by 1 exists
Fluorination partial pressure is 3kPa, and then nitrogen partial pressure exists the fiber static immersing after fluorination directly to carry out fluorination treatment under 30kPa
Concentration is dries after being reacted 40 minutes in the ethanol solution of 1.5% (3- aminopropyls) trimethoxy silane, then static leaching
Bubble hydrolysis in pH=4 aqueous hydrochloric acid solution is dried after 60 minutes, and it is 1.5% that fiber finally is put into concentration
Immersion reaction is dried after 20 minutes in the ethanol solution of (3- aminopropyls) trimethoxy silane.
The aramid fiber II fibers of the high composite performance of gained are added into epoxy resin-base and prepare corresponding composite, gained is multiple
The correlated performance of condensation material is seen attached list.
Embodiment 10
First will be by monomer mole ratio TPC:PDA:PABZ=10:5:Aramid III fiber prepared by 5 is disclosed with prior art
Method fluorination partial pressure be 5kPa, nitrogen partial pressure be 55kPa under directly progress fluorination treatment, then the fiber after fluorination is moved
State is continuously immersed in reaction in the ethanol solution of (3- aminopropyls) trimethoxy silane that concentration is 5% and dried after 1 minute, connects
Dynamic to be continuously immersed in hydrolysis in pH=2 aqueous hydrochloric acid solution and dried after 0.3 minute, finally dynamically connect fiber
It is continuous to be for drying after being reacted 1 minute in the ethanol solution of 8% 3- glycidyl ether oxygen propyl trimethoxy silicanes by concentration
Can.
The aramid III fiber of the high composite performance of gained is added into epoxy resin-base and prepares corresponding composite, gained
The correlated performance of composite is seen attached list.
Embodiment 11
First will be by monomer mole ratio TPC:PDA:PABZ=10:5:Aramid III fiber prepared by 5 is disclosed with prior art
Method fluorination partial pressure be 4kPa, nitrogen partial pressure be 40kPa under directly progress fluorination treatment, then the fiber after fluorination is moved
State is continuously immersed in reaction in the ethanol solution of (3- aminopropyls) triethoxysilane that concentration is 10% and dried after 0.5 minute
Dry, then dynamic is continuously immersed in hydrolysis in pH=2 oxalic acid aqueous solution and dried after 1 minute, finally moves fiber
After state continues through concentration for reaction in the ethanol solution of 5% 3- glycidoxypropyltrietandysilane andysilanes 0.5 minute
Drying.
The aramid III fiber of the high composite performance of gained is added into epoxy resin-base and prepares corresponding composite, gained
The correlated performance of composite is seen attached list.
Embodiment 12
First will be by monomer mole ratio TPC:PDA:PABZ=10:5:Aramid III fiber prepared by 5 is disclosed with prior art
Method fluorination partial pressure be 4kPa, nitrogen partial pressure be 40kPa under directly progress fluorination treatment, then the fiber after fluorination is moved
State is continuously immersed in reaction in the ethanol solution of (3- aminopropyls) triethoxysilane that concentration is 4% and dried after 0.8 minute
Dry, then dynamic is continuously immersed in hydrolysis in pH=5 formic acid and oxalic acid aqueous solution and dried after 0.5 minute, finally
Reacted in the ethanol solution that fiber is dynamically continued through to the 3- glycidoxypropyltrietandysilane andysilanes that concentration is 10%
Dried after 0.7 minute.
The aramid III fiber of the high composite performance of gained is added into epoxy resin-base and prepares corresponding composite, gained
The correlated performance of composite is seen attached list.
Embodiment 13
First will be by monomer mole ratio TPC:PDA:PABZ=10:5:Aramid III fiber prepared by 5 is disclosed with prior art
Method fluorination partial pressure be 5kPa, nitrogen partial pressure be 50kPa under directly progress fluorination treatment, then the fiber after fluorination is moved
State is continuously immersed in reaction in the ethanol solution of (3- aminopropyls) triethoxysilane that concentration is 1% and dried after 0.1 minute,
Then dynamic is continuously immersed in hydrolysis in pH=1 aqueous hydrochloric acid solution and dried after 0.1 minute, finally by fiber dynamic
Reaction in the ethanol solution for the 3- glycidyl ether oxygen propyl trimethoxy silicanes that concentration is 20% is continued through to dry after 0.1 minute
It is dry.
The aramid III fiber of the high composite performance of gained is added into epoxy resin-base and prepares corresponding composite, gained
The correlated performance of composite is seen attached list.
Embodiment 14
First will be by monomer mole ratio TPC:PDA:PABZ=10:5:Aramid III fiber prepared by 5 is disclosed with prior art
Method fluorination partial pressure be 3kPa, nitrogen partial pressure be 30kPa under directly progress fluorination treatment, then the fiber after fluorination is moved
State continues through the ethanol solution of (3- aminopropyls) methyldiethoxysilane that concentration is 20% and dried after reacting 0.1 minute
Dry, then dynamic is continuously immersed in hydrolysis in pH=4 aqueous solution of nitric acid and dried after 1.5 minutes, finally by fiber
Dynamic continues through concentration to dry after reacting 1.8 minutes in the ethanol solution of 2% (3- aminopropyls) trimethoxy silane
.
The aramid III fiber of the high composite performance of gained is added into epoxy resin-base and prepares corresponding composite, gained
The correlated performance of composite is seen attached list.
Embodiment 15
First will be by monomer mole ratio TPC:PDA:PABZ=10:5:Aramid III fiber prepared by 5 is disclosed with prior art
Method fluorination partial pressure be 5kPa, nitrogen partial pressure be 50kPa under directly progress fluorination treatment, then the fiber after fluorination is moved
State continues through the ethanol solution of (3- aminopropyls) methyldiethoxysilane that concentration is 16% and dried after reacting 0.3 minute
Dry, then dynamic is continuously immersed in hydrolysis in pH=2 aqueous hydrochloric acid solution and dried after 0.4 minute, finally by fiber
Dynamic continues through concentration to dry after reacting 0.3 minute in the ethanol solution of 15% (3- aminopropyls) trimethoxy silane
.
The aramid III fiber of the high composite performance of gained is added into epoxy resin-base and prepares corresponding composite, gained
The correlated performance of composite is seen attached list.
Embodiment 16
First will be by monomer mole ratio TPC:PDA:PABZ=10:5:Aramid III fiber prepared by 5 is disclosed with prior art
Method fluorination partial pressure be 5kPa, nitrogen partial pressure be 50kPa under directly progress fluorination treatment, then the fiber after fluorination is moved
State continues through the ethanol solution of (3- aminopropyls) triethoxysilane that concentration is 2% and dried after reacting 1.5 minutes, connects
Dynamic continuously to be immersed in hydrolysis in pH=4 oxalic acid aqueous solution and dried after 2 minutes, it is finally that fiber is dynamically continuous
It is drying after being reacted 2 minutes in the ethanol solution of 1% (3- aminopropyls) trimethoxy silane by concentration.
The aramid III fiber of the high composite performance of gained is added into epoxy resin-base and prepares corresponding composite, gained
The correlated performance of composite is seen attached list.
Embodiment 17
First will be by monomer mole ratio TPC:PDA:PABZ=10:5:Aramid III fiber prepared by 5 is disclosed with prior art
Method fluorination partial pressure be 4kPa, nitrogen partial pressure be 40kPa under directly progress fluorination treatment, then the fiber after fluorination is moved
State continues through the ethanol solution of (3- aminopropyls) triethoxysilane that concentration is 8% and dried after reacting 1 minute, then
Dynamic is continuously immersed in hydrolysis in pH=3 oxalic acid aqueous solution is dried after 0.8 minute, finally that fiber is dynamically continuous
It is for drying after being reacted 0.6 minute in the ethanol solution of 10% (3- aminopropyls) methyldiethoxysilane by concentration
Can.
The aramid III fiber of the high composite performance of gained is added into epoxy resin-base and prepares corresponding composite, gained
The correlated performance of composite is seen attached list.
Embodiment 18
First will be by monomer mole ratio TPC:PDA:PABZ=10:5:Aramid III fiber prepared by 5 is disclosed with prior art
Method fluorination partial pressure be 5kPa, nitrogen partial pressure be 50kPa under directly progress fluorination treatment, then the fiber after fluorination is moved
State continues through the ethanol solution of (3- aminopropyls) triethoxysilane that concentration is 10% and reacted 0.6 minute, then moves
State is continuously immersed in hydrolysis in pH=4 aqueous formic acid and dried after 1 minute, finally dynamically continues through fiber
Concentration is drying after being reacted 0.8 minute in the ethanol solution of 6% 3- glycidyl ether oxygen propyl trimethoxy silicanes.
Embodiment 19
First will be by monomer mole ratio DAR:TPA=1:Polyparaphenylene's Benzo-dioxazole fiber prior art prepared by 1
Disclosed method is 5kPa in fluorination partial pressure, and nitrogen partial pressure is directly carries out fluorination treatment under 60kPa, then by the fibre after fluorination
Tie up static immersing reaction in ethanol solution of the concentration for 1% (3- aminopropyls) triethoxysilane to dry after 8 minutes, connect
Static immersing hydrolysis in pH=4 oxalic acid aqueous solution to be dried after 5 minutes, fiber finally is put into concentration is
Immersion reaction is dried after 110 minutes in the ethanol solution of 0.5% vinyltrimethoxy silane.
Polyparaphenylene's Benzo-dioxazole fiber of the high composite performance of gained is added into maleic anhydride resin matrix to prepare accordingly
Composite, the correlated performance of gained composite sees attached list.
Embodiment 20
First will be by monomer mole ratio DAR:TPA=1:Polyparaphenylene's Benzo-dioxazole fiber prior art prepared by 1
Disclosed method is 3kPa in fluorination partial pressure, and nitrogen partial pressure is directly carries out fluorination treatment under 30kPa, then by the fibre after fluorination
Static immersing reaction in ethanol solution of the concentration for 2% (3- aminopropyls) trimethoxy silane is tieed up to dry after 30 minutes,
Then static immersing hydrolysis in pH=4 formic acid and acetic acid mixed aqueous solution is dried after 40 minutes, finally by fibre
Dimension is put into immersion reaction in the ethanol solution for the VTES that concentration is 5% and dried after 1 minute.
Polyparaphenylene's Benzo-dioxazole fiber of the high composite performance of gained is added into maleic anhydride resin matrix to prepare accordingly
Composite, the correlated performance of gained composite sees attached list.
Embodiment 21
First will be by monomer mole ratio DAR:TPA=1:Polyparaphenylene's Benzo-dioxazole fiber prior art prepared by 1
Disclosed method is 4kPa in fluorination partial pressure, and nitrogen partial pressure is directly carries out fluorination treatment under 40kPa, then by the fibre after fluorination
Static immersing reaction in ethanol solution of the concentration for 1.5% (3- aminopropyls) trimethoxy silane is tieed up to dry after 20 minutes
Dry, then static immersing hydrolysis in pH=4 aqueous hydrochloric acid solution is dried after 30 minutes, is finally put into fiber dense
Immersion reaction in the ethanol solution for 1% VTES is spent to dry after 30 minutes.
Polyparaphenylene's Benzo-dioxazole fiber of the high composite performance of gained is added into maleic anhydride resin matrix to prepare accordingly
Composite, the correlated performance of gained composite sees attached list.
Embodiment 22
First will be by monomer mole ratio DAR:TPA=1:Polyparaphenylene's Benzo-dioxazole fiber prior art prepared by 1
Disclosed method is 3kPa in fluorination partial pressure, and nitrogen partial pressure is directly carries out fluorination treatment under 40kPa, then by the fibre after fluorination
Static immersing reaction in ethanol solution of the concentration for 1.5% (3- aminopropyls) trimethoxy silane is tieed up to dry after 30 minutes
Dry, then static immersing hydrolysis in pH=4 aqueous hydrochloric acid solution is dried after 30 minutes, is finally put into fiber dense
Immersion reaction in the ethanol solution for 2% VTES is spent to dry after 30 minutes.
Polyparaphenylene's Benzo-dioxazole fiber of the high composite performance of gained is added into maleic anhydride resin matrix to prepare accordingly
Composite, the correlated performance of gained composite sees attached list.
Embodiment 23
First will be by monomer mole ratio DAR:TPA=1:Polyparaphenylene's Benzo-dioxazole fiber prior art prepared by 1
Disclosed method is 4kPa in fluorination partial pressure, and nitrogen partial pressure is directly carries out fluorination treatment under 40kPa, then by the fibre after fluorination
Static immersing reaction in ethanol solution of the concentration for 2% (3- aminopropyls) trimethoxy silane is tieed up to dry after 40 minutes,
Then static immersing hydrolysis in pH=4 aqueous hydrochloric acid solution is dried after 30 minutes, and fiber finally is put into concentration
Dried for immersion reaction in the ethanol solution of 1% vinyltrimethoxy silane after 40 minutes.
Polyparaphenylene's Benzo-dioxazole fiber of the high composite performance of gained is added into maleic anhydride resin matrix to prepare accordingly
Composite, the correlated performance of gained composite sees attached list.
Embodiment 24
First will be by monomer mole ratio DAR:TPA=1:Polyparaphenylene's Benzo-dioxazole fiber prior art prepared by 1
Disclosed method is 3kPa in fluorination partial pressure, and nitrogen partial pressure is directly carries out fluorination treatment under 40kPa, then by the fibre after fluorination
Static immersing reaction in ethanol solution of the concentration for 2% (3- aminopropyls) trimethoxy silane is tieed up to dry after 40 minutes,
Then static immersing hydrolysis in pH=4 oxalic acid aqueous solution is dried after 30 minutes, and fiber finally is put into concentration
Dried for immersion reaction in the ethanol solution of 4% vinyltrimethoxy silane after 40 minutes.
Polyparaphenylene's Benzo-dioxazole fiber of the high composite performance of gained is added into maleic anhydride resin matrix to prepare accordingly
Composite, the correlated performance of gained composite sees attached list
Comparative example 1
Will be by monomer mole ratio TPC according to the same method of embodiment 1 and technique:PDA:PABZ=10:5:5 prepare
Aramid III fiber body without any surface treatment.
The obtained aramid III fiber body without any surface treatment is added into epoxy resin-base to prepare accordingly again
Condensation material, the correlated performance of gained composite is seen attached list.
Comparative example 2
Will be by monomer mole ratio TPC according to the same method of embodiment 1 and technique:PDA:PABZ=10:5:5 virtues prepared
Synthetic fibre III fibers carry out direct fluorination treatment.
The aramid III fiber of obtained direct fluorination treatment is added into epoxy resin-base and prepares corresponding composite,
The correlated performance of gained composite is seen attached list.
Comparative example 3
Will be by monomer mole ratio TPC according to the same method of embodiment 1 and technique:PDA:PABZ=10:5:5 virtues prepared
Synthetic fibre III fibers directly carry out fluorination treatment, wherein fluorination partial pressure is 120KPa, nitrogen partial pressure is 400KPa.
The aramid III fiber of obtained direct fluorination treatment is added into epoxy resin-base and prepares corresponding composite,
The correlated performance of gained composite is seen attached list.
Comparative example 4
This comparative example is after the aramid III fiber for preparing comparative example 1 is handled its surface with plasma, then
The corresponding composite prepared to epoxy resin-base.The correlated performance of gained composite is seen attached list.
Comparative example 5
Will be by monomer mole ratio TPC according to the same method of embodiment 7 and technique:PDA=1:1 prepares without any
The aramid fiber II fiber bodies of surface treatment.
The obtained aramid fiber II fiber bodies without any surface treatment are added into epoxy resin-base to prepare accordingly again
Condensation material, the correlated performance of gained composite is seen attached list.
Comparative example 6
Will be by monomer mole ratio DAR according to the same method of embodiment 18 and technique:TPA=1:1 prepares without appointing
Polyparaphenylene's Benzo-dioxazole fiber bodies of what surface treatment.
Obtained polyparaphenylene's Benzo-dioxazole fiber bodies without any surface treatment are added into maleic anhydride resin
Matrix prepares corresponding composite, and the correlated performance of gained composite is seen attached list.
Comparative example 7
Will be by monomer mole ratio DAR according to the same method of embodiment 18 and technique:TPA=1:1 prepares polyparaphenylene's benzene
Bing bis- oxazole fiber bodies.Polyparaphenylene's Benzo-dioxazole fiber is subjected to direct fluorination treatment, handling process and embodiment again
20 is identical.
Polyparaphenylene's Benzo-dioxazole fiber bodies of obtained direct fluorination treatment are added into maleic anhydride resin matrix
Corresponding composite is prepared, the correlated performance of gained composite is seen attached list.
Claims (6)
1. a kind of preparation method of high composite performance aromatic polymer fiber, the processing step and condition of this method is as follows：
1) aromatic polymer fiber is directly carried out to the aromatic polymer fibre that fluorinated surface processing obtains surface group containing C-F
Dimension, wherein fluorine gas partial pressure are 0.5~5kPa, and nitrogen partial pressure is 5~60kPa, and nitrogen partial pressure is at least 10 times of fluorination partial pressure,
Aromatic polymer fiber used is Fanglun 1414, heteroaromatic Fypro or polyparaphenylene's benzene
Any of Bing bis- oxazole fibers；
2) under normal temperature, by the aromatic polymer fiber static immersing of surface group containing C-F mass percent concentration be 0.1~
1~120min is reacted in the ethanol solution of 5% silane coupler containing amino, or dynamic continues through mass percent concentration
Ethanol solution for 1~20% silane coupler containing amino simultaneously reacts 0.1~2min, and then drying contains to surface
The aromatic polymer fiber of siloxy；
3) under normal temperature, the aromatic polymer fiber static immersing of siloxy is contained into the acidic aqueous solution that pH is 1~6 in surface
1~120min of middle hydrolysis, or dynamic continue through the acidic aqueous solution that pH is 1~6 and hydrolyze 0.1~2min, and then drying is
It can obtain aromatic polymer fiber of the surface containing silicone hydroxyl；
4) under normal temperature, by aromatic polymer fiber static immersing of the surface containing silicone hydroxyl mass percent concentration be 0.1~
1~120min is reacted in the ethanol solution of 5% silane coupler containing amino, epoxy radicals or pi-allyl, or dynamic is continued through
Mass percent concentration for 1~20% silane coupler containing amino, epoxy radicals or pi-allyl ethanol solution and react 0.1~
2min, then aromatic polymer fiber of the drying to high composite performance.
2. the preparation method of high composite performance aromatic polymer fiber according to claim 1, the 2) step of this method
The mass percent concentration of the ethanol solution of the silane coupler containing amino is 0.8~2% used in middle static immersing, during immersion
Between be 20~60min；The mass percent concentration of the ethanol solution of silane coupler containing amino used in dynamic continuous processing
For 4~10%, processing time is 0.5~1min；Silane coupler containing amino used is (3- aminopropyls) dimethyl second
TMOS, (3- aminopropyls) methyldiethoxysilane, (3- aminopropyls) triethoxysilane and (3- aminopropyls)
At least one of trimethoxy silane.
3. the preparation method of high composite performance aromatic polymer fiber according to claim 1 or 2, the 3) step of this method
The pH of acidic aqueous solution described in rapid is 3~5；Static immersing hydrolysis time is 20~60min；The dynamic continuous hydrolysis time is
0.5~1min；Acidic aqueous solution used is that inorganic acid or organic acid are formulated, and inorganic acid is sulfuric acid, hydrochloric acid, phosphoric acid and nitre
At least one of at least one of acid, the preferred formic acid of organic acid, acetic acid and oxalic acid.
4. the preparation method of high composite performance aromatic polymer fiber according to claim 1 or 2, the 4) step of this method
The mass percent concentration of the ethanol solution of the silane coupler containing amino, epoxy radicals or pi-allyl is used in static immersing in rapid
0.8~2%, soak time is 20~60min；Dynamic continuous processing is used containing the silane coupled of amino, epoxy radicals or pi-allyl
The mass percent concentration of the ethanol solution of agent is 4~10%, and processing time is 0.5~1min；Used contains amino, epoxy radicals
Or the silane coupler of pi-allyl is (3- aminopropyls) dimethylethoxysilane, (3- aminopropyls) methyl diethoxy silicon
Alkane, (3- aminopropyls) triethoxysilane, (3- aminopropyls) trimethoxy silane, 3- glycidyl ether oxygen propyl trimethoxies
Base silane, 3- glycidoxypropyltrietandysilane andysilanes, 3- glycydoxy methyl diethoxies silicon, ethene
Any of base trimethoxy silane or VTES.
5. the preparation method of high composite performance aromatic polymer fiber according to claim 3, the 4) step of this method
The mass percent concentration of the ethanol solution of the silane coupler containing amino, epoxy radicals or pi-allyl is used in middle static immersing
0.8~2%, soak time is 20~60min；Dynamic continuous processing is used containing the silane coupled of amino, epoxy radicals or pi-allyl
The mass percent concentration of the ethanol solution of agent is 4~10%, and processing time is 0.5~1min；Used contains amino, epoxy radicals
Or the silane coupler of pi-allyl is (3- aminopropyls) dimethylethoxysilane, (3- aminopropyls) methyl diethoxy silicon
Alkane, (3- aminopropyls) triethoxysilane, (3- aminopropyls) trimethoxy silane, 3- glycidyl ether oxygen propyl trimethoxies
Base silane, 3- glycidoxypropyltrietandysilane andysilanes, 3- glycydoxy methyl diethoxies silicon, ethene
Any of base trimethoxy silane or VTES.
6. a kind of aromatic polymer fiber of the high composite performance prepared by claim 1 methods described, the fiber surface contains
Have and the reactive active group of matrix resin, its infrared display 1000-1100cm-1There is the peak of Si-O-Si keys at place, in X-ray
The 103.6eV of photoelectron spectroscopy figure, which is combined at energy, Si element energy spectral peaks, with the PPTA wherein prepared
The interlaminar shear strength of fiber and the composite of epoxy resin formation is 38-45MPa, and impregnation silk intensity is 4.0-4.5GPa；
Interlaminar shear strength with the heteroaromatic Fypro wherein prepared and the composite of epoxy resin formation is 52-60MPa,
Impregnation silk intensity is 5.4-6.0GPa；With the polyparaphenylene's Benzo-dioxazole fiber wherein prepared and maleic anhydride resin formation
The interlaminar shear strength of composite is 36-48MPa, and impregnation silk intensity is 5.2-5.8GPa.
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| CN108330564A (en) * | 2018-02-07 | 2018-07-27 | 湖州科博信息科技有限公司 | A kind of high-performance heatproof textile fabric and its preparation process |
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