CN104911895B - Polyparaphenylene benzo dioxazole fiber containing fluorine on surface and preparation method thereof - Google Patents
Polyparaphenylene benzo dioxazole fiber containing fluorine on surface and preparation method thereof Download PDFInfo
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- CN104911895B CN104911895B CN201510324307.1A CN201510324307A CN104911895B CN 104911895 B CN104911895 B CN 104911895B CN 201510324307 A CN201510324307 A CN 201510324307A CN 104911895 B CN104911895 B CN 104911895B
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Abstract
The invention discloses a polyparaphenylene benzo dioxazole fiber containing fluorine on surface, which is prepared through the following steps: the body of the polyparaphenylene benzo dioxazole fiber is treated by using a hydrogen fluoride gas, then is mixed by using fluorine/oxygen/inert gas, is subjected to fluoridation for 10 seconds to 2 hours at 5-150 DEG C, and finally is stored in air atmosphere for at least one hour. A contact angle between the surface of the obtained fiber and water is 60-90 degrees, the interlaminar shear strength of a composite material prepared from the fiber and epoxy resin is 30-45MPa, the tensile strength of an impregnated filament is 5.0-5.3GPa, and the tensile modulus is 264-280GPa. The polyparaphenylene benzo dioxazole fiber containing fluorine on surface is high in surface activity, interfacial interaction between the fiber and matrix resin is strong, the interlaminar shear strength of the composite material prepared by using the fiber can be improved by 50-125%, the tensile strength of the impregnated filament is improved by 4-10%, and the modulus is improved by 10-16%. According to the invention, the fluorination rate is high, the treatment time is short, the process is simple and controllable, the cost is relatively low, and the fiber has relatively strong application prospect.
Description
Technical field
The invention belongs to polyparaphenylene's Benzo-dioxazole (PBO) fiber and its preparing technical field, and in particular to Yi Zhongbiao
Fluorine-containing polyparaphenylene's Benzo-dioxazole (PBO) fiber in face and preparation method thereof.
Background technology
Because the aircraft component of fibre-reinforced polymer matrix composites integrated design manufacture is than using traditional gold
The aircraft component that category material and mode are manufactured can not only mitigate weight 20-30%, and also compare metal material using with maintenance cost
Material reduces 15-25%, thus is widely used in aerospace field.It is reported that, current polymer matrix composites exist
Consumption in aircraft is up to more than the 50% of its construction weight.
Although fibre-reinforced polymer matrix composites are widely applied due to its light weight in aerospace field,
But its mechanical property can't fully meet the requirement that aerospace field is used.And affect fibre-reinforced resin base composite wood
Material mechanical property reason mainly has two aspects：One be reinforcing fiber itself mechanical property it is high not enough；Two is reinforcing fiber
It is not strong with the interfacial interaction of matrix resin.And reinforcing fiber is not strong with the interfacial interaction of matrix resin, but mainly with
Reinforcing fiber surface activity is relevant.Thus, in the case that reinforcing fiber chemical constitution is certain, to improve the property of composite
Can, such as the mechanical strength of composite, interlaminar shear strength etc., it is necessary to the activity on reinforcing fiber surface is improved, to improve
Reinforcing fiber surface and the interaction force of resin boundary surface.
Polyparaphenylene's Benzo-dioxazole (PBO) fiber has become at present preparation boat as a kind of high strength and modulus fiber
The amplified medium of empty space flight advanced composite material.The fiber is existed by 4,6- diamino resorcin hydrochlorates and p-phthalic acid
Heated polymerization in polyphosphoric acids solvent obtains liquid crystal polymer stock solution, then the spinning work such as Jing filtrations, deaeration, spinning, heat treatment
Pbo fiber of the tensile strength that skill is obtained more than 4.5GPa.When the resin-made with the fiber as amplified medium, based on epoxy resin
The interlaminar shear strength of the standby composite for obtaining only has 20MPa or so, it is impossible to meet aeronautical and space technology development multiple to such
The higher technical requirements that the composite performance of condensation material is proposed.
Improve fiber surface activity at present, improve the main method bag on its surface and matrix resin interfacial interaction power
Include：Methods of chemical treatment such as corona method, plasma method, alkali or acid etc., but these processing methods all exist it is such or like that bright
Aobvious deficiency.The surface activity decay of the pbo fiber after such as being processed with corona method and plasma method is very fast, activity stability
Not enough；Often can be larger to fiber Effect on Mechanical Properties itself after being processed with chemical methodes such as alkali or acid, and be unsuitable for large-scale
Accelerated surface process.And the pbo fiber after these methods process, it is unsatisfactory to the reinforced effects of polymer matrix composites.
Direct surface fluorination treatment technology is a kind of effective surface modifying method that in recent years fast development is got up, and it is
Surface is carried out to high polymer as fluorination reagent by the use of the fluorine gas of high reaction activity to be modified, and the surface fluorination polymer of its preparation
Material has low cost, because only on surface forming nanometer layer, the advantages of do not affect the mechanical property of polymeric material body.It is main at present
It is used to be surface-treated polyolefin polymers, to improve the barrier property of TPO container.Can also be used in addition
Activation processing is carried out to material surfaces such as polyolefin, can adhesive property with improve its surface.Such as US72255561,
US2006118988, CN1717438A etc. disclose the method that some oxygen fluorinated surfaces are processed.These methods are mainly using sky
Oxygen and fluorine gas gaseous mixture in gas is processed material surface.Although the material surface Jing after oxygen fluorination treatment, its surface
Activity and shear bond strength significantly improve, but due in air contain certain moisture content, thus in fluorination process produce fluorine
Changing after hydrogen is combined with water can cause heavy corrosion to fluorizating apparatus.In order to solve these problems, CN101798748B employs nothing
Oxygen is fluorinated, although the problems such as can overcoming equipment corrosion, because, without oxygen, oxygen is to fluorination reaction speed in fluorine gas gaseous mixture
Inhibitory action disappear, make so as to cause fluorination rates too high fiber surface chemical composition uniformity and repeatability it is not easily-controllable
System.In addition, have document disclose polymer in C=N easily by strong oxidizer oxidation (Liao J H, Li Q F, Rudbeck H C,
et al.Oxidative degradation of polybenzimidazole membranes as electrolytes
for high temperature proton exchange membrane fuel cells[J].Fuel Cells,2011,
11(6):745-755.).Due to containing substantial amounts of C=N keys in pbo fiber macromolecular chain, and fluorine gas is just a kind of strong
Oxidant, thus whether pure fluorination or oxygen fluorination all easily cause polymer macromolecule chain interruption, affect fiber table itself
The mechanical property in face, and the composite material interface that the mechanical properties decrease on fiber surface itself can cause it standby with resin-made is in
It is now weak interface, is unfavorable for the raising of composite property.Therefore, how to ensure that pbo fiber surface macromolecular chain breaks after fluorination
Split less, to ensure that the mechanical strength and then raising composite performance of composite material interface layer itself are always this area and are difficult to solve
Problem.
The content of the invention
The primary and foremost purpose of the present invention is to provide a kind of polyparaphenylene's benzo of fluorine-contained surface for the deficiencies in the prior art
The preparation method of Er oxazoles (PBO) fiber.
It is a further object of the present invention to provide a kind of fluorine-contained surface polyparaphenylene's Benzo-dioxazole prepared by said method
(PBO) fiber.
The preparation method of polyparaphenylene's Benzo-dioxazole fiber of the fluorine-contained surface that the present invention is provided, the method is first will be poly-
Penylene Benzo-dioxazole fiber bodies are placed in closed vacuum reactor, then evacuation, and use nitrogen displacement reactor
In after remaining air, hydrogen fluoride gas are first filled with vacuum reactor, process 3-10 minutes, be re-filled with fluorine gas/oxygen/lazy
Property gas mixture, and be warming up to 5～150 DEG C and carry out fluorination treatment 30 seconds～2 hours, finally by polyparaphenylene's Benzo-dioxazole
Fiber is deposited at least 1 hour in air atmosphere, that is, obtain polyparaphenylene's Benzo-dioxazole fiber of fluorine-contained surface, or
The air being first sufficiently displaced from nitrogen in tubular reactor, then connects polyparaphenylene's Benzo-dioxazole fiber bodies
Continuous to pass through tubular reactor, the one end for entering tubular type fire door in fiber is continually fed into hydrogen fluoride gas, in fiber tubular type fire door one is gone out
End is continually fed into the gaseous mixture of oxygen/fluorine gas/noble gases, and stops at 5～150 DEG C 10 seconds～1 hour, then will winding
Fiber deposit at least 1 hour in air atmosphere, that is, obtain polyparaphenylene's Benzo-dioxazole fiber of fluorine-contained surface,
Wherein fluohydric acid gas partial pressure in the reactor remains 0.01～10KPa, preferably 0.1～5KPa；Fluorine gas is in reaction
Partial pressure in device remains 0.1～100KPa, preferably 5～60KPa；Oxygen partial pressure in the reactor remains 0.01～
30KPa, preferably 1～10KPa；Noble gases partial pressure in the reactor remains 1～400KPa, preferably 50～240KPa.
In said method, fluorine gas/oxygen/noble gases gaseous mixture used is by fluorine gas and oxygen and nitrogen, argon, helium
Any one composition in gas and carbon dioxide.
In said method, the temperature that polyparaphenylene's Benzo-dioxazole fiber is placed in into airtight vacuum reactor fluorination treatment is excellent
25～100 DEG C are selected, preferably 2 minutes～0.5 hour time of fluorination treatment.
In said method, the temperature that polyparaphenylene's Benzo-dioxazole fiber is continued through into tubular reactor fluorination treatment is excellent
25～100 DEG C are selected, preferably 1 minute～0.5 hour time of fluorination treatment.
In said method, polyparaphenylene's Benzo-dioxazole fiber bodies used are by 4,6-diaminoresorcinol hydrochloric acid
Salt and p-phthalic acid polyphosphoric acids solvent it is heated be polymerized, spinning is prepared from, chemical constitution is as follows：
Wherein 4,6- diamino resorcin hydrochlorates and the mol ratio of p-phthalic acid are 1:1.
Polyparaphenylene's Benzo-dioxazole fiber bodies used in said method are the fibre for not carrying out any surface treatment
The fiber after peacekeeping using plasma, corona or chemical method for treating surface process.
Polyparaphenylene's Benzo-dioxazole fiber of the fluorine-contained surface prepared by said method that the present invention is provided, the fiber
Carbon-fluorine covalent bond structure and carboxylic, oh group are contained in surface, and its attenuated total reflectance infrared spectrogram is in 1100～1300cm-1Have
The absworption peak of carbon-fluorine covalent bond；3100～3500cm-1Between broad peak and 1708cm-1Nearby there are hydroxyl and carboxylic group in peak
Absworption peak, in 1274cm-1There are the O-C=N absworption peaks of benzoxazole ring at place, combines in the 698eV of x-ray photoelectron energy spectrum diagram
There is fluorine element energy spectral peak at energy, its surface is 60-90 degree with the contact angle of water；Using prepared by the fiber and epoxy resin being combined
The interlaminar shear strength of material is 30-45MPa, and impregnation silk tensile strength is 5.0-5.3GPa, and stretch moduluses are 265-280GPa.
The present invention compared with prior art, has the advantages that：
1st, because the pbo fiber that the present invention is provided is to introduce carbon-fluorine polar covalent bond, carboxyl and hydroxyl on its surface
The high-strength high-modulus fibre of structure, thus it has not only filled up the blank of the pbo fiber currently without fluorine-contained surface structure, and can be bright
The activity on aobvious increase pbo fiber surface, is significantly increased the interfacial interaction of the pbo fiber and matrix resin, enhances
The mechanical property of polymer matrix composites.
2nd, due to the present invention provide method be first pbo fiber to be processed with hydrogen fluoride gas, using fluohydric acid gas with
C=N can form stronger electron interaction in pbo fiber macromole, as shown in Figure 3, C=N double bonds be served necessarily
Protective effect so that during the course of the reaction fluorine gas is not easy to be easier attack phenyl ring into Gong oxazole rings, thus can weaken fluorine
Effect of the gas to C=N, on the one hand can reduce the decline of the fiber surface layer mechanical strength caused because of C=N bond fissions, separately
On the one hand more polar groups can be formed on surface layer macromolecular chain phenyl ring, substantially increases and provide fiber shape with the present invention
Into composite interlaminar shear strength (50～125% can be improved).
3rd, the oxygen in the gaseous mixture used in the method provided due to the present invention is not to utilize the oxygen in air, thus
Not moisture vapor, the fluohydric acid gas for being allowed to be produced in fluorination process can not be combined with water, and to fluorizating apparatus heavy corrosion is caused, can
Extend the service life of fluorizating apparatus.
4th, because the method that the present invention is provided is used with oxygenous and noble gases fluorine gas gaseous mixtures to pbo fiber
Surface carries out fluorination treatment, thus not only can efficiently generate carbon-fluorine bond in fiber surface, can also in a large number produce carboxylic, hydroxyl base
Group, gives the high activity on pbo fiber surface, while oxygen has certain inhibitory action to fluorination reaction speed so that fiber
The uniformity and repeatability of surface chemistry composition is relatively easy to control, and the addition of noble gases, can to a certain extent reduce anti-again
Concentration of fluorine in answering, prevents the peril produced because concentration of fluorine is too high.
5th, because the present invention is to enter not fluorine-containing pbo fiber with fluorine gas/oxygen/noble gases under certain process conditions
Row surface fluorination chemical reaction not only can neatly prepare surface preparing by the control to direct flaorination process
The Series P BO fiber of different fluorinated volumes, different surfaces activity, and process is simple is controllable, and cost is relatively low, with stronger application
Prospect.
The Common surface processing methods such as the method for chemical treatment such as 6 and corona method, plasma method, alkali or acid are compared, this
The activity stability of the fiber surface after bright method process is good, and the mechanical property of the composite for preparing is more excellent.
Description of the drawings
Fig. 1 is the attenuated total reflectance infrared spectrogram (ATR- of the fluorine-contained surface pbo fiber obtained by the embodiment of the present invention 11
FTIR), wave-number range is 1100～1300cm in figure-1It is the absworption peak of carbon-fluorine covalent bond；3100cm-1～3500cm-1Between
Broad peak and 1708cm-1Nearby peak is the absworption peak of hydroxyl and carboxylic group, in 1274cm-1Place is the O-C of benzoxazole ring
=N absworption peaks.
Fig. 2 is fluorine-contained surface pbo fiber x-ray photoelectron energy spectrum diagram (XPS) obtained by the embodiment of the present invention 11, in figure
The peak that 698eV combinations can be located is fluorine element energy spectral peak.
Fig. 3 is the electron interaction that C=N is formed with fluohydric acid gas (HF) in the pbo fiber macromolecular chain that the present invention is adopted
Schematic diagram.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that be that following examples are only used
In being further described to the present invention, it is impossible to be interpreted as limiting the scope of the invention, the people that is skilled in technique in the field
Some nonessential modifications and adaptations that member makes according to the content of the invention described above, still fall within protection scope of the present invention.
In addition what deserves to be explained is, 1) the following examples and surface activity of fiber is connect using static state obtained in comparative example
As a result the size of feeler is seen attached list representing.2) to the reinforced effects of composite materials property it is with ring after its surface treatment
The interlaminar shear strength of the dependence test that resin is carried out based on epoxy resin system, wherein composite uses NOL rings
Method, the tensile strength and modulus of impregnation silk are tested according to GBT3362-2005, and test result sees attached list.
Embodiment 1
First polyparaphenylene's Benzo-dioxazole fiber bodies are placed in closed vacuum reactor, then evacuation, is used in combination
After air in nitrogen displacement reactor three times, hydrogen fluoride gas are first filled with vacuum reactor, process 3 minutes, then to true
Fluorine gas/oxygen/nitrogen gaseous mixture is filled with empty reactor, fluohydric acid gas partial pressure in the reactor is controlled for 1KPa, fluorine gas partial pressure
For 10KPa, oxygen partial pressure 1KPa, nitrogen partial pressure 50KPa, and heat up 25 DEG C and carry out fluorination treatment 20 minutes, finally will be poly- to benzene
Support Benzo-dioxazole fiber deposits at least 1 hour in air atmosphere.
The fluorine-containing pbo fiber for obtaining addition epoxy resin-base is prepared into corresponding composite, gained composite
Correlated performance sees attached list.
Embodiment 2
First polyparaphenylene's Benzo-dioxazole fiber bodies are placed in closed vacuum reactor, then evacuation, is used in combination
After air in nitrogen displacement reactor three times, hydrogen fluoride gas are first filled with vacuum reactor, process 5 minutes, then to true
Fluorine gas/oxygen/argon gaseous mixture is filled with empty reactor, fluohydric acid gas partial pressure in the reactor is controlled for 4KPa, fluorine gas partial pressure
For 60KPa, oxygen partial pressure 6KPa, partial pressure of ar gas 240KPa, and heat up 50 DEG C and carry out fluorination treatment 5 minutes, finally will be poly- to benzene
Support Benzo-dioxazole fiber deposits at least 1 hour in air atmosphere.
The fluorine-containing pbo fiber for obtaining addition epoxy resin-base is prepared into corresponding composite, gained composite
Correlated performance sees attached list.
Embodiment 3
First polyparaphenylene's Benzo-dioxazole fiber bodies are placed in closed vacuum reactor, then evacuation, is used in combination
After air in nitrogen displacement reactor three times, hydrogen fluoride gas are first filled with vacuum reactor, process 10 minutes, then to true
Fluorine gas/oxygen/helium gaseous mixture is filled with empty reactor, fluohydric acid gas partial pressure in the reactor is controlled for 0.01KPa, fluorine gas point
Press as 0.5KPa, oxygen partial pressure 0.05KPa, helium partial pressure 5KPa, and heat up 100 DEG C and carry out fluorination treatment 2 hours, finally will be poly-
At least 1 hour is deposited in air atmosphere to penylene Benzo-dioxazole fiber.
The fluorine-containing pbo fiber for obtaining addition epoxy resin-base is prepared into corresponding composite, gained composite
Correlated performance sees attached list.
Embodiment 4
First polyparaphenylene's Benzo-dioxazole fiber bodies are placed in closed vacuum reactor, then evacuation, is used in combination
After air in nitrogen displacement reactor three times, hydrogen fluoride gas are first filled with vacuum reactor, process 6 minutes, then to true
Fluorine gas/oxygen/carbon dioxide gaseous mixture is filled with empty reactor, control fluohydric acid gas in the reactor partial pressure be 0.8KPa, fluorine gas
Partial pressure is 6KPa, oxygen partial pressure 5KPa, carbon dioxide partial pressure 20KPa, and heats up 120 DEG C and carry out fluorination treatment 40 minutes, finally
Polyparaphenylene's Benzo-dioxazole fiber is deposited at least 1 hour in air atmosphere.
The fluorine-containing pbo fiber for obtaining addition epoxy resin-base is prepared into corresponding composite, gained composite
Correlated performance sees attached list.
Embodiment 5
First polyparaphenylene's Benzo-dioxazole fiber bodies are placed in closed vacuum reactor, then evacuation, is used in combination
After air in nitrogen displacement reactor three times, hydrogen fluoride gas are first filled with vacuum reactor, process 7 minutes, then to true
Fluorine gas/oxygen/nitrogen gaseous mixture is filled with empty reactor, in the reactor partial pressure is 0.1KPa to control fluohydric acid gas, and fluorine gas is anti-
Answer in device partial pressure to be 0.1KPa, oxygen partial pressure 0.01KPa, nitrogen partial pressure 1KPa, and heat up 150 DEG C and carry out fluorination treatment 50 seconds,
Finally polyparaphenylene's Benzo-dioxazole fiber is deposited at least 1 hour in air atmosphere.
The fluorine-containing pbo fiber for obtaining addition epoxy resin-base is prepared into corresponding composite, gained composite
Correlated performance sees attached list.
Embodiment 6
First polyparaphenylene's Benzo-dioxazole fiber bodies are placed in closed vacuum reactor, then evacuation, is used in combination
After air in nitrogen displacement reactor three times, hydrogen fluoride gas are first filled with vacuum reactor, process 4 minutes, then to true
Fluorine gas/oxygen/nitrogen gaseous mixture is filled with empty reactor, in the reactor partial pressure is 5KPa to control fluohydric acid gas, and fluorine gas partial pressure is
60KPa, oxygen partial pressure 30KPa, nitrogen partial pressure 100KPa, and fluorination treatment is carried out at 5 DEG C 2 minutes, finally by polyparaphenylene
Benzo-dioxazole fiber deposits at least 1 hour in air atmosphere.
The fluorine-containing pbo fiber for obtaining addition epoxy resin-base is prepared into corresponding composite, gained composite
Correlated performance sees attached list.
Embodiment 7
First polyparaphenylene's Benzo-dioxazole fiber bodies are placed in closed vacuum reactor, then evacuation, is used in combination
After air in nitrogen displacement reactor three times, hydrogen fluoride gas are first filled with vacuum reactor, process 4 minutes, then to true
Fluorine gas/oxygen/nitrogen gaseous mixture is filled with empty reactor, in the reactor partial pressure is 8KPa to control fluohydric acid gas, and fluorine gas partial pressure is
80KPa, oxygen partial pressure 10KPa, nitrogen partial pressure 300KPa, and heat up 120 DEG C and carry out fluorination treatment 30 seconds, finally by polyparaphenylene
Benzo-dioxazole fiber deposits at least 1 hour in air atmosphere.
The fluorine-containing pbo fiber for obtaining addition epoxy resin-base is prepared into corresponding composite, gained composite
Correlated performance sees attached list.
Embodiment 8
First polyparaphenylene's Benzo-dioxazole fiber bodies are placed in closed vacuum reactor, then evacuation, is used in combination
After air in nitrogen displacement reactor three times, hydrogen fluoride gas are first filled with vacuum reactor, process 4 minutes, then to true
Fluorine gas/oxygen/nitrogen gaseous mixture is filled with empty reactor, in the reactor partial pressure is 10KPa to control fluohydric acid gas, and fluorine gas partial pressure is
100KPa, oxygen partial pressure 20KPa, nitrogen partial pressure 400KPa, and fluorination treatment is carried out at 10 DEG C 0.5 hour, finally will be poly- right
Penylene Benzo-dioxazole fiber deposits at least 1 hour in air atmosphere.
The fluorine-containing pbo fiber for obtaining addition epoxy resin-base is prepared into corresponding composite, gained composite
Correlated performance sees attached list.
Embodiment 9
The air being first sufficiently displaced from nitrogen in tubular reactor, then connects polyparaphenylene's Benzo-dioxazole fiber bodies
Continuous to pass through tubular reactor, the one end for entering tubular type fire door in fiber is continually fed into hydrogen fluoride gas, in fiber tubular type fire door one is gone out
End is continually fed into the gaseous mixture of oxygen/fluorine gas/noble gases, and stops at being warmed up to 120 DEG C 10 seconds, finally by the fiber of winding
At least 1 hour is deposited in air atmosphere.Hydrogen fluoride gas partial pressure is 5KPa, and fluorine gas partial pressure is 50KPa, and oxygen partial pressure is
5KPa, helium partial pressure is 400KPa.
The fluorine-containing pbo fiber for obtaining addition epoxy resin-base is prepared into corresponding composite, gained composite
Correlated performance sees attached list.
Embodiment 10
The air being first sufficiently displaced from nitrogen in tubular reactor, then connects polyparaphenylene's Benzo-dioxazole fiber bodies
Continuous to pass through tubular reactor, the one end for entering tubular type fire door in fiber is continually fed into hydrogen fluoride gas, in fiber tubular type fire door one is gone out
End is continually fed into the gaseous mixture of oxygen/delivery of fluorine/nitrogen, and stops at 100 DEG C 30 seconds, finally by the fiber of winding in air atmosphere
Enclose middle storage at least 1 hour.Hydrogen fluoride gas partial pressure is 7KPa, and fluorine gas partial pressure is 60KPa, and oxygen partial pressure is 15KPa, and nitrogen divides
Press as 240KPa.
The fluorine-containing pbo fiber for obtaining addition epoxy resin-base is prepared into corresponding composite, gained composite
Correlated performance sees attached list.
Embodiment 11
The air being first sufficiently displaced from nitrogen in tubular reactor, then connects polyparaphenylene's Benzo-dioxazole fiber bodies
Continuous to pass through tubular reactor, the one end for entering tubular type fire door in fiber is continually fed into hydrogen fluoride gas, in fiber tubular type fire door one is gone out
End is continually fed into the gaseous mixture of oxygen/delivery of fluorine/nitrogen, and stops at 30 DEG C 1 hour, finally by the fiber of winding in air atmosphere
Enclose middle storage at least 1 hour.Hydrogen fluoride gas partial pressure is 0.5KPa, and fluorine gas partial pressure is 5KPa, and oxygen partial pressure is 10KPa, nitrogen
Partial pressure is 5KPa.
The fluorine-containing pbo fiber for obtaining addition epoxy resin-base is prepared into corresponding composite, gained composite
Correlated performance sees attached list.
Embodiment 12
The air being first sufficiently displaced from nitrogen in tubular reactor, then connects polyparaphenylene's Benzo-dioxazole fiber bodies
Continuous to pass through tubular reactor, the one end for entering tubular type fire door in fiber is continually fed into hydrogen fluoride gas, in fiber tubular type fire door one is gone out
End is continually fed into the gaseous mixture of oxygen/fluorine gas/helium, and stops at 100 DEG C 1 minute, finally by the fiber of winding in air
At least 1 hour is deposited in atmosphere.Hydrogen fluoride gas partial pressure is 5KPa, and fluorine gas partial pressure is 80KPa, and oxygen partial pressure is 2KPa, helium
Partial pressure is 300KPa.
The fluorine-containing pbo fiber for obtaining addition epoxy resin-base is prepared into corresponding composite, gained composite
Correlated performance sees attached list.
Embodiment 13
The air being first sufficiently displaced from nitrogen in tubular reactor, then connects polyparaphenylene's Benzo-dioxazole fiber bodies
Continuous to pass through tubular reactor, the one end for entering tubular type fire door in fiber is continually fed into hydrogen fluoride gas, in fiber tubular type fire door one is gone out
End is continually fed into the gaseous mixture of oxygen/fluorine gas/argon, and stops at 50 DEG C 40 minutes, finally by the fiber of winding in air
At least 1 hour is deposited in atmosphere.Hydrogen fluoride gas partial pressure is 0.1KPa, and fluorine gas partial pressure is 0.3KPa, and oxygen partial pressure is 0.1KPa,
Partial pressure of ar gas is 3KPa.
The fluorine-containing pbo fiber for obtaining addition epoxy resin-base is prepared into corresponding composite, gained composite
Correlated performance sees attached list.
Embodiment 14
The air being first sufficiently displaced from nitrogen in tubular reactor, then connects polyparaphenylene's Benzo-dioxazole fiber bodies
Continuous to pass through tubular reactor, the one end for entering tubular type fire door in fiber is continually fed into hydrogen fluoride gas, in fiber tubular type fire door one is gone out
End is continually fed into the gaseous mixture of oxygen/delivery of fluorine/nitrogen, and stops at 25 DEG C 0.5 hour, finally by the fiber of winding in air
At least 1 hour is deposited in atmosphere.Hydrogen fluoride gas partial pressure is 3KPa, and fluorine gas partial pressure is 20KPa, and oxygen partial pressure is 6KPa, nitrogen
Partial pressure is 100KPa.
The fluorine-containing pbo fiber for obtaining addition epoxy resin-base is prepared into corresponding composite, gained composite
Correlated performance sees attached list.
Embodiment 15
The air being first sufficiently displaced from nitrogen in tubular reactor, then connects polyparaphenylene's Benzo-dioxazole fiber bodies
Continuous to pass through tubular reactor, the one end for entering tubular type fire door in fiber is continually fed into hydrogen fluoride gas, in fiber tubular type fire door one is gone out
End is continually fed into the gaseous mixture of oxygen/delivery of fluorine/nitrogen, and stops at 40 DEG C 10 minutes, finally by the fiber of winding in air
At least 1 hour is deposited in atmosphere.Hydrogen fluoride gas partial pressure is 1KPa, and fluorine gas partial pressure is 10KPa, and oxygen partial pressure is 1KPa, nitrogen
Partial pressure is 50KPa.
The fluorine-containing pbo fiber for obtaining addition epoxy resin-base is prepared into corresponding composite, gained composite
Correlated performance sees attached list.
Embodiment 16
The air being first sufficiently displaced from nitrogen in tubular reactor, then connects polyparaphenylene's Benzo-dioxazole fiber bodies
Continuous to pass through tubular reactor, the one end for entering tubular type fire door in fiber is continually fed into hydrogen fluoride gas, in fiber tubular type fire door one is gone out
End is continually fed into the gaseous mixture of oxygen/delivery of fluorine/nitrogen, and stops at 10 DEG C 20 minutes, finally by the fiber of winding in air
At least 1 hour is deposited in atmosphere.Hydrogen fluoride gas partial pressure is 0.03KPa, and fluorine gas partial pressure is 0.1KPa, and oxygen partial pressure is
0.5KPa, nitrogen partial pressure is 1KPa.
The fluorine-containing pbo fiber for obtaining addition epoxy resin-base is prepared into corresponding composite, gained composite
Correlated performance sees attached list.
Comparative example 1
By 4,6- diamino resorcin hydrochlorates and p-phthalic acid in molar ratio 1:1 in polyphosphoric acids solvent Jing add
The polyparaphenylene's Benzo-dioxazole fiber bodies without any surface treatment obtained by thermal polymerization, conventional spinning preparation.
Epoxy resin-base is added to prepare corresponding composite wood the pbo fiber body without any surface treatment for obtaining
Material, the correlated performance of gained composite sees attached list.
Comparative example 2
First polyparaphenylene's Benzo-dioxazole fiber bodies are placed in closed vacuum reactor, then evacuation, is used in combination
After air in nitrogen displacement reactor three times, fluorine gas/oxygen/nitrogen gaseous mixture is filled with vacuum reactor, controls fluorine gas
Partial pressure is 10KPa, oxygen partial pressure 1KPa, nitrogen partial pressure 50KPa, and heats up 25 DEG C and carry out fluorination treatment 20 minutes, finally will be poly-
At least 1 hour is deposited in air atmosphere to penylene Benzo-dioxazole fiber.
The fluorine-containing pbo fiber for obtaining addition epoxy resin-base is prepared into corresponding composite, gained composite
Correlated performance sees attached list.
Comparative example 3
This comparative example is after the pbo fiber for preparing comparative example 1 is processed its surface with plasma, then with ring
The corresponding composite that epoxy resin-based body is prepared.
The Jing plasma surface treatment pbo fiber for obtaining addition epoxy resin-base is prepared into corresponding composite,
The correlated performance of gained composite sees attached list.
Table
Claims (10)
1. the preparation method of polyparaphenylene's Benzo-dioxazole fiber of a kind of fluorine-contained surface, the method is first by polyparaphenylene's benzo
Er oxazole fiber bodies are placed in closed vacuum reactor, then evacuation, and with remaining sky in nitrogen displacement reactor
After gas, hydrogen fluoride gas are first filled with vacuum reactor, process 3-10 minutes, be re-filled with fluorine gas/oxygen/noble gases mixing
Gas, and be warming up to 5～150 DEG C and carry out fluorination treatment 30 seconds～2 hours, finally by polyparaphenylene's Benzo-dioxazole fiber in air
Deposit in atmosphere at least 1 hour, that is, obtain polyparaphenylene's Benzo-dioxazole fiber of fluorine-contained surface, or
The air being first sufficiently displaced from nitrogen in tubular reactor, then continuously leads to polyparaphenylene's Benzo-dioxazole fiber bodies
Tubular reactor is crossed, the one end for entering tubular type fire door in fiber is continually fed into hydrogen fluoride gas, go out tubular type fire door one in fiber and support
The continuous gaseous mixture for being passed through fluorine gas/oxygen/noble gases, and stop at 5～150 DEG C 10 seconds～1 hour, then by the fibre of winding
Dimension is deposited at least 1 hour in air atmosphere, that is, obtain polyparaphenylene's Benzo-dioxazole fiber of fluorine-contained surface,
Wherein hydrogen fluoride gas partial pressure in the reactor remains 0.01～10KPa；Fluorine gas partial pressure in the reactor keeps
For 0.1～100KPa；Oxygen partial pressure in the reactor remains 0.01～30KPa；Noble gases partial pressure in the reactor
Remain 1～400KPa.
2. the preparation method of polyparaphenylene's Benzo-dioxazole fiber of fluorine-contained surface according to claim 1, in the method
Fluorine gas/oxygen/noble gases gaseous mixture used is by fluorine gas and oxygen and nitrogen, argon, helium and carbon dioxide
Any one composition.
3. the preparation method of polyparaphenylene's Benzo-dioxazole fiber of fluorine-contained surface according to claim 1 and 2, the method
Middle fluohydric acid gas partial pressure in the reactor remains 0.1～5KPa；Fluorine gas partial pressure in the reactor remains 5～60KPa；Oxygen
Gas partial pressure in the reactor remains 1～10KPa；Noble gases partial pressure in the reactor remains 50～240KPa.
4. the preparation method of polyparaphenylene's Benzo-dioxazole fiber of fluorine-contained surface according to claim 1 and 2, the method
The middle temperature that polyparaphenylene's Benzo-dioxazole fiber is placed in airtight vacuum reactor fluorination treatment is 25～100 DEG C, at fluorination
The time of reason is 2 minutes～0.5 hour；Polyparaphenylene's Benzo-dioxazole fiber is continued through into tubular reactor fluorination treatment
Temperature is 25～100 DEG C, and the time of fluorination treatment is 1 minute～0.5 hour.
5. the preparation method of polyparaphenylene's Benzo-dioxazole fiber of fluorine-contained surface according to claim 3, in the method
It is 25～100 DEG C by the temperature that polyparaphenylene's Benzo-dioxazole fiber is placed in airtight vacuum reactor fluorination treatment, fluorination treatment
Time be 2 minutes～0.5 hour；Polyparaphenylene's Benzo-dioxazole fiber is continued through into the temperature of tubular reactor fluorination treatment
Spend for 25～100 DEG C, the time of fluorination treatment is 1 minute～0.5 hour.
6. the preparation method of polyparaphenylene's Benzo-dioxazole fiber of fluorine-contained surface according to claim 1 and 2, the method
In handled polyparaphenylene's Benzo-dioxazole fiber bodies be do not carry out any surface treatment the fiber and using etc. from
The fiber after the process of daughter, corona or chemical method for treating surface.
7. the preparation method of polyparaphenylene's Benzo-dioxazole fiber of fluorine-contained surface according to claim 3, in the method
Handled polyparaphenylene's Benzo-dioxazole fiber bodies are not carry out the fiber of any surface treatment and adopted plasma
The fiber after the process of body, corona or chemical method for treating surface.
8. the preparation method of polyparaphenylene's Benzo-dioxazole fiber of fluorine-contained surface according to claim 4, in the method
Handled polyparaphenylene's Benzo-dioxazole fiber bodies are not carry out the fiber of any surface treatment and adopted plasma
The fiber after the process of body, corona or chemical method for treating surface.
9. the preparation method of polyparaphenylene's Benzo-dioxazole fiber of fluorine-contained surface according to claim 5, in the method
Handled polyparaphenylene's Benzo-dioxazole fiber bodies are not carry out the fiber of any surface treatment and adopted plasma
The fiber after the process of body, corona or chemical method for treating surface.
10. it is a kind of by claim 1 methods described prepare fluorine-contained surface polyparaphenylene's Benzo-dioxazole fiber, the fiber
Carbon-fluorine covalent bond structure and carboxylic, oh group are contained in surface, and its attenuated total reflectance infrared spectrogram is in 1100～1300cm-1Have
The absworption peak of carbon-fluorine covalent bond；3100～3500cm-1Between broad peak and 1708cm-1Nearby there are hydroxyl and carboxylic group in peak
Absworption peak, in 1274cm-1There are the O-C=N absworption peaks of benzoxazole ring at place, combines in the 698eV of x-ray photoelectron energy spectrum diagram
There is fluorine element energy spectral peak at energy, its surface is 60-90 degree with the contact angle of water；Using prepared by the fiber and epoxy resin being combined
The interlaminar shear strength of material is 30-45MPa, and impregnation silk tensile strength is 5.0-5.3GPa, and stretch moduluses are 265-280GPa.
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| CN102587058A (en) * | 2012-02-28 | 2012-07-18 | 四川大学 | Direct fluorination method for producing surface fluorine-containing fiber |
| CN103224576A (en) * | 2013-04-28 | 2013-07-31 | 四川大学 | Fluorine rubber with high fluorine content on surface, and preparation method thereof |
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| CN102587058A (en) * | 2012-02-28 | 2012-07-18 | 四川大学 | Direct fluorination method for producing surface fluorine-containing fiber |
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