CN103820996B - A kind of preparation method of binary graft modification pbo fiber - Google Patents
A kind of preparation method of binary graft modification pbo fiber Download PDFInfo
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Abstract
A kind of preparation method of binary graft modification pbo fiber, the present invention relates to a kind of preparation method of pbo fiber, it will solve existing pbo fiber surface and causes in inertia with matrix resin wettability difference and cause pbo fiber molecular chain rupture by elemental oxygen, the problem that fibrous mechanical property declines.Preparation method: one, graphene oxide functionalization; Two, activation processing is carried out to pbo fiber; Three, pbo fiber joins in Lithium Aluminium Hydride-ether saturated solution and carries out hydroxy functionalized process; Four, in pbo fiber surface A PTMS grafting; Five, pbo fiber surface oxidation Graphene binary grafting.APTMS and graphene oxide are incorporated into pbo fiber surface by chemical graft process by the present invention simultaneously, improve the wettability of pbo fiber, make the binary grafting pbo fiber obtained can keep higher TENSILE STRENGTH under the shock of elemental oxygen.The present invention is mainly used in the preparation of pbo fiber.
Description
Technical field
The present invention relates to a kind of preparation method of pbo fiber.
Background technology
PBO (polyparaphenylene's benzo-dioxazole) fiber is by the obtained a kind of high-performance fiber of fiber spinning from crystalline state, has excellent mechanical property, heat resistance and fire resistance, is described as " super fiber of 21 century ".But the skin-core structure of pbo fiber makes its surface in inertia, poor with resin matrix wettability, thus causes the interface bond strength of composite low, seriously constrain its application in the composite.
The structure of pbo fiber is as follows:
In the Low Earth Orbit space environment apart from earth surface 200 ~ 700km height, there is the factors such as elemental oxygen, ultraviolet irradiation, electronics, proton, micrometeor and space junk.Wherein, the factor that elemental oxygen is most important, the most dangerous beyond doubt.When spacecraft flies with the speed of 8km/s, its surface atom oxygen atom line can reach 10
12~ 10
16atom/cm
2s.Under this speed, the average impact energy of elemental oxygen is 4 ~ 5eV, and this energy is enough to the chemical bond of many materials is ruptured, thus causes declining to a great extent of material physical property.Pbo fiber/epoxy resin composite material is widely used as spacecraft construction material due to advantages such as its high specific strength, high ratio modulus and light weights.But as polymer matrix composite, pbo fiber/epoxy resin composite material is as easy as rolling off a log is subject to atomic oxygen erosion.Can constantly be subject to the circulation that colds and heat succeed each other when spacecraft runs in Low Earth Orbit, pbo fiber because the different meeting of thermal coefficient of expansion forms high thermal stress in their interface, thus produces many micro-cracks from epoxy resin-base.Elemental oxygen corrodes the weak interface junction of composite by micro-crack, can cause pbo fiber heavy corrosion, even rupture, and then causes the mechanical property of composite to decline to a great extent.
The protective coating that organosilicon is used as spacecraft surface is widely applied.The organosilicon be exposed in atomic oxygen environment can form glassy silica, can play a good protection to primer.APTMS commonly uses organo silane coupling agent as one can not only improve fiber interface performance effectively, and the silicon oxygen bond structure of itself has good resistivity to elemental oxygen.Graphene, as the hardest material of current nature, has the hot property of great surface area, abundant functional group and excellence, has been widely used in preparation high-performance, multifunctional nano composite material by people.The Graphene obtained by oxidizing process has certain fault of construction, and as the wild phase of composite, the existence of these faults of construction can improve the interfacial interaction between Graphene and matrix material, thus improves the interface performance of composite.
Chemical graft process becomes the study hotspot of Material Field in recent years as a kind of method preparing multi-scale reinforcing body of newly opening up, and becomes the important research direction of fiber surface modification gradually.The method utilizes carboxyl derivatization reaction (chloride, esterification), mercaptan coupling reaction etc. by polymer graft to fiber surface, has that cost is low, the process time is shorter and the feature such as modified effect is remarkable.
Summary of the invention
The object of the invention is to solve existing pbo fiber surface cause in inertia with matrix resin wettability difference and cause pbo fiber molecular chain rupture by elemental oxygen, the problem that fibrous mechanical property declines, and the preparation method of a kind of APTMS provided and graphene oxide binary grafting pbo fiber.
The preparation method of binary graft modification pbo fiber of the present invention follows these steps to realize:
One, graphene oxide functionalization: by 10ml ~ 100ml thionyl chloride and 1ml ~ 5mlN, dinethylformamide joins in single port flask, pour 0.1g ~ 0.4g graphene oxide powder subsequently into, and sonic oscillation 0.5h ~ 2h, then hot reflux 12h ~ 72h is added in a nitrogen atmosphere, last decompression distillation, until solvent removal, obtains the graphene oxide of functionalization;
Two, pbo fiber activation processing: pbo fiber is wrapped on square glass framework, be immersed in sulfuric acid solution, at room temperature stir process 1h ~ 4h, after taking out, use deionized water to wash 1 time ~ 7 times, finally dry 10min ~ 60min at 80 DEG C ~ 150 DEG C, obtains activating pbo fiber;
Three, the hydroxy functionalized process of pbo fiber: 0.02g ~ 0.08g is activated pbo fiber and joins in 25ml ~ 100ml Lithium Aluminium Hydride-ether saturated solution, add hot reflux 0.5h ~ 2h under nitrogen protection, spend deionized water subsequently 1 time ~ 7 times, dry 10min ~ 60min at 80 DEG C ~ 150 DEG C, obtains hydroxy functionalized pbo fiber again;
Four, pbo fiber surface A PTMS grafting: the APTMS (3-aminopropyl-trimethoxy silane) of 0.5ml ~ 2ml to be joined in 50ml ~ 150ml absolute ethyl alcohol and to mix, add the hydroxy functionalized pbo fiber of 0.02g ~ 0.08g subsequently, stir process 6h ~ 24h at 30 DEG C ~ 60 DEG C, then use absolute ethanol washing 1 time ~ 7 times, drying process obtains the pbo fiber of APTMS grafting;
Five, pbo fiber surface oxidation Graphene binary grafting: the graphene oxide of 0.05g ~ 0.15g functionalization is dissolved in 40ml ~ 100mlN; in dinethylformamide; and sonic oscillation 1h ~ 3h; add the pbo fiber of 0.02g ~ 0.08gAPTMS grafting subsequently; reflux heating 24h ~ 72h under nitrogen protection; use DMF washing the fibre 1 time ~ 7 times, after drying process, obtain binary graft modification pbo fiber.
APTMS and graphene oxide are incorporated into pbo fiber surface by chemical graft process by the present invention simultaneously, due to the graphene oxide of fiber surface can obviously increase fiber surface roughness and and resin matrix between contact area, thus form powerful mechanical lock and make a concerted effort.In addition; the a large amount of polar functional group of surface of graphene oxide can improve the wettability of pbo fiber; the interface shear strength of the binary grafting pbo fiber obtained is made to reach more than 65MPa; simultaneously due to the protective effect of binary graft fibres surface A PTMS silicone layer; when elemental oxygen open-assembly time reaches 36h; its binary grafting pbo fiber stretching strength retentivity is 51.5%, and the stretching strength retentivity of this modification pbo fiber is apparently higher than untreated pbo fiber.
Accompanying drawing explanation
Fig. 1 is the SEM surface topography map of the pbo fiber of the APTMS grafting that embodiment one step 4 obtains;
Fig. 2 is the SEM surface topography map of the binary graft modification pbo fiber that embodiment one obtains;
Fig. 3 is the block diagram of two kinds of pbo fiber interface shear strengths;
Fig. 4 is the stretching strength retentivity curve map of pbo fiber under different elemental oxygen open-assembly time, and a represents untreated pbo fiber, and b represents binary graft modification pbo fiber.
Detailed description of the invention
Detailed description of the invention one: the preparation method of present embodiment binary graft modification pbo fiber follows these steps to realize:
One, graphene oxide functionalization: by 10ml ~ 100ml thionyl chloride and 1ml ~ 5mlN, dinethylformamide joins in single port flask, pour 0.1g ~ 0.4g graphene oxide powder subsequently into, and sonic oscillation 0.5h ~ 2h, then hot reflux 12h ~ 72h is added in a nitrogen atmosphere, last decompression distillation, until solvent removes completely, obtains the graphene oxide of functionalization;
Two, pbo fiber activation processing: pbo fiber is wrapped on square glass framework, be immersed in sulfuric acid solution, at room temperature stir process 1h ~ 4h, after taking out, use deionized water to wash 1 time ~ 7 times, finally dry 10min ~ 60min at 80 DEG C ~ 150 DEG C, obtains activating pbo fiber;
Three, the hydroxy functionalized process of pbo fiber: 0.02g ~ 0.08g is activated pbo fiber and joins in 25ml ~ 100ml Lithium Aluminium Hydride-ether saturated solution, add hot reflux 0.5h ~ 2h under nitrogen protection, spend deionized water subsequently 1 time ~ 7 times, dry 10min ~ 60min at 80 DEG C ~ 150 DEG C, obtains hydroxy functionalized pbo fiber again;
Four, pbo fiber surface A PTMS grafting: the APTMS of 0.5ml ~ 2ml to be joined in 50ml ~ 150ml absolute ethyl alcohol and to mix, add the hydroxy functionalized pbo fiber of 0.02g ~ 0.08g subsequently, stir process 6h ~ 24h at 30 DEG C ~ 60 DEG C, then use absolute ethanol washing 1 time ~ 7 times, drying process obtains the pbo fiber of APTMS grafting;
Five, pbo fiber surface oxidation Graphene binary grafting: the graphene oxide of 0.05g ~ 0.15g functionalization is dissolved in 40ml ~ 100mlN; in dinethylformamide; and sonic oscillation 1h ~ 3h; add the pbo fiber of 0.02g ~ 0.08gAPTMS grafting subsequently; reflux heating 24h ~ 72h under nitrogen protection; use DMF washing the fibre 1 time ~ 7 times, after drying process, obtain binary graft modification pbo fiber.
The process for preparation of the Lithium Aluminium Hydride described in present embodiment step 3-ether saturated solution joins in 100ml ~ 150ml absolute ether by 20g ~ 30g Lithium Aluminium Hydride, and at room temperature strong agitation is to dissolving completely, i.e. obtained Lithium Aluminium Hydride-ether saturated solution.
The heating-up temperature heated in reflow treatment in a nitrogen atmosphere described in present embodiment step one is 70 DEG C ~ 90 DEG C.
The cost of the preparation method of present embodiment binary graft modification pbo fiber is lower, and reaction condition is gentle, and reactions steps is relatively succinct, while significantly improving pbo fiber interface performance, can effectively solve a difficult problem for its anti-atomic oxygen erosion performance difference.
Detailed description of the invention two: present embodiment and detailed description of the invention one are carry out at the temperature of 40 DEG C ~ 70 DEG C unlike the decompression distillation described in step one.Other step and parameter identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment and detailed description of the invention one or two are 20% ~ 80% unlike the sulfuric acid solution mass fraction described in step 2.Other step and parameter identical with detailed description of the invention one or two.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three are 100r/min ~ 300r/min unlike the speed stirred in step 2 at room temperature stir process.Other step and parameter identical with one of detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four are dry 10min ~ 60min at 50 DEG C ~ 100 DEG C unlike the drying process described in step 4.Other step and parameter identical with one of detailed description of the invention one to four.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five are dry 10min ~ 60min at 100 DEG C ~ 200 DEG C unlike the drying process described in step 5.Other step and parameter identical with one of detailed description of the invention one to five.
Embodiment one: the preparation method of the present embodiment binary graft modification pbo fiber follows these steps to realize:
One, graphene oxide functionalization: 85ml thionyl chloride and 4mlN, dinethylformamide joins in single port flask, pour 0.25g graphene oxide powder subsequently into, and sonic oscillation 1h, then reflux 48h at nitrogen atmosphere 70 DEG C, finally at 50 DEG C, decompression distillation, until solvent removes completely, obtains the graphene oxide of functionalization;
Two, pbo fiber activation processing: first pbo fiber is wrapped on square glass framework, then being immersed in mass fraction is in the sulfuric acid of 60%, 3h is processed under the condition of room temperature and mixing speed 150r/min, deionized water is used by fiber to wash 5 times, finally dry 30min at 100 DEG C, obtains activating pbo fiber;
Three, the hydroxy functionalized process of pbo fiber: 0.05g is activated pbo fiber and join in 50ml Lithium Aluminium Hydride-ether saturated solution, add hot reflux 1h under nitrogen protection, spend deionized water subsequently 5 times, finally dry 30min at 100 DEG C, obtains hydroxy functionalized pbo fiber;
Four, pbo fiber surface A PTMS grafting: the APTMS of 0.5ml to be joined in 50ml absolute ethyl alcohol and to mix, add the hydroxy functionalized pbo fiber of 0.05g subsequently, stir process 12h at 45 DEG C, fiber is used absolute ethanol washing 5 times, finally dry 30min at 100 DEG C, obtains the pbo fiber of APTMS grafting;
Five, pbo fiber surface oxidation Graphene binary grafting: the graphene oxide of 0.1g functionalization is dissolved in 50mlN; in dinethylformamide; and sonic oscillation 2h; add the pbo fiber of 0.05gAPTMS grafting subsequently; reflux heating 48h under nitrogen protection, uses DMF to wash 5 times by fiber; finally dry 30min at 150 DEG C, obtains binary graft modification pbo fiber.
Fig. 1 is the SEM surface topography map of the pbo fiber of the APTMS grafting that step 4 obtains, as we can see from the figure, the nonwoven fabric from filaments that fiber surface has one deck fine and close, coarse, this from level to level shape thing be exactly the APTMS being grafted on pbo fiber surface.It can not only provide active reaction point for next step graphene oxide grafting, and the silicon oxygen bond structure of itself effectively can resist the erosion of elemental oxygen.
Fig. 2 is the SEM surface topography map of the APTMS for preparing of this embodiment and graphene oxide binary grafting pbo fiber, and as we can see from the figure, the graphene oxide sheet laminating of fold is attached to pbo fiber surface.This illustrates that graphene oxide successfully grafts on pbo fiber surface, has prepared a kind of novel multi-scale reinforcing body, has confirmed the feasibility of this binary grafting method.
Fig. 3 is pbo fiber interface shear strength test result.As we can see from the figure, the interface shear strength of binary grafting pbo fiber is 65.3MPa, and the interface shear strength of untreated pbo fiber is 40.4MPa, and compared with untreated pbo fiber, the interface shear strength of binary grafting pbo fiber improves 61.6%.This be due to the graphene oxide of fiber surface can obviously increase fiber surface roughness and and resin matrix between contact area, thus form powerful mechanical lock and make a concerted effort.In addition, a large amount of polar functional group of surface of graphene oxide can improve the wettability of pbo fiber, contributes to the interface performance improving fiber equally.
The test process of wherein pbo fiber/epoxy resin interface performance is as follows:
First, with two-sided tape, PBO filament is fixed on sample holder, then epoxy resin E-51 and 3 is taken with the ratio of 100:32,3-diethyl 4,4-diaminodiphenyl-methane curing agent, being coated in equably after both are mixed on PBO filament, being cured with being placed in baking oven; Finally, composite material interface performance evaluation tester (FA-620, Japanese Dong Rong Co., Ltd.) is used to test the interface shear strength (IFSS) between the pbo fiber after before modified and epoxy resin-base.Often kind of condition surveys about 40 resin balls, finally calculates interface shear strength mean value.IFSS computing formula is as follows:
In formula: F
maxfor unsticking power, N; D represents fibre diameter, m; L is the embedding length of resin balls, m.
Fig. 4 is the stretching strength retentivity curve of pbo fiber under different elemental oxygen open-assembly time, and wherein, curve a and b is that untreated pbo fiber and binary grafting pbo fiber expose the stretching strength retentivity after experiment through elemental oxygen respectively.As we can see from the figure with the increase of elemental oxygen open-assembly time, because elemental oxygen is to the extremely strong corrosion function of pbo fiber, its strand is ruptured, thus causes TENSILE STRENGTH to decline rapidly.When elemental oxygen open-assembly time reaches 36h, the stretching strength retentivity of untreated pbo fiber is only 40%; For binary grafting pbo fiber; when elemental oxygen open-assembly time reaches 36h; its stretching strength retentivity is 51.5%, and due to the protective effect of binary graft fibres surface A PTMS silicone layer, the stretching strength retentivity of fiber is apparently higher than untreated pbo fiber.
The test process that its induced by atomic oxygen exposes experiment is as follows:
The device that elemental oxygen exposure test adopts is BJ University of Aeronautics & Astronautics's THE FILAMENT DISCHARGE AND magnetically confined type (IFM) ground-based simulation equipment.Experiment condition is temperature 60 ~ 70 DEG C, vacuum pressure 1.4 × 10
-1pa, elemental oxygen energy 0.01 ~ 0.05eV, atomic oxygen flux density 8.02 × 10
15atoms/cm
2s.This experiment have chosen different elemental oxygen open-assembly time 4h, 8h, 12h, 16h, 20h, 24h, 28h, 32h and 36h.Then, pbo fiber and binary grafting pbo fiber through exposing experiment are carried out TENSILE STRENGTH test, thus obtains the stretching strength retentivity of fiber.
Embodiment two: the preparation method of the present embodiment binary graft modification pbo fiber follows these steps to realize:
One, graphene oxide functionalization: 80ml thionyl chloride and 3mlN, dinethylformamide joins in single port flask, pour 0.2g graphene oxide powder subsequently into, and sonic oscillation 2h, then reflux 36h at nitrogen atmosphere 75 DEG C, finally at 45 DEG C, decompression distillation, until solvent removes completely, obtains the graphene oxide of functionalization;
Two, pbo fiber activation processing: first pbo fiber is wrapped on square glass framework, then being immersed in mass fraction is in the sulfuric acid of 65%, 3h is processed under the condition of room temperature and mixing speed 200r/min, deionized water is used by fiber to wash 6 times, finally dry 60min at 100 DEG C, obtains activating pbo fiber;
Three, the hydroxy functionalized process of pbo fiber: 0.03g is activated pbo fiber and join in 75ml Lithium Aluminium Hydride-ether saturated solution, add hot reflux 1.5h under nitrogen protection, spend deionized water subsequently 6 times, finally dry 60min at 100 DEG C, obtains hydroxy functionalized pbo fiber;
Four, pbo fiber surface A PTMS grafting: the APTMS of 1ml to be joined in 100ml absolute ethyl alcohol and to mix, add the hydroxy functionalized pbo fiber of 0.03g subsequently, stir process 24h at 40 DEG C, fiber is used absolute ethanol washing 6 times, finally dry 60min at 60 DEG C, obtains the pbo fiber of APTMS grafting;
Five, pbo fiber surface oxidation Graphene binary grafting: the graphene oxide of 0.03g functionalization is dissolved in 40mlN; in dinethylformamide; and sonic oscillation 1h; add the pbo fiber of 0.03gAPTMS grafting subsequently; reflux heating 36h under nitrogen protection, uses DMF to wash 6 times by fiber; finally dry 60min at 120 DEG C, obtains binary graft modification pbo fiber.
The interface shear strength of the binary graft modification pbo fiber that the present embodiment obtains is 57.8MPa, and compared with untreated pbo fiber, the interface shear strength of binary grafting pbo fiber improves 43.1%.
Claims (6)
1. a preparation method for binary graft modification pbo fiber, is characterized in that the preparation method of binary graft modification pbo fiber follows these steps to realize:
One, graphene oxide functionalization: by 10ml ~ 100ml thionyl chloride and 1ml ~ 5mlN, dinethylformamide joins in single port flask, pour 0.1g ~ 0.4g graphene oxide powder subsequently into, and sonic oscillation 0.5h ~ 2h, then hot reflux 12h ~ 72h is added in a nitrogen atmosphere, last decompression distillation, until solvent removal, obtains the graphene oxide of functionalization;
Two, pbo fiber activation processing: pbo fiber is wrapped on square glass framework, be immersed in sulfuric acid solution, at room temperature stir process 1h ~ 4h, after taking out, use deionized water to wash 1 time ~ 7 times, finally dry 10min ~ 60min at 80 DEG C ~ 150 DEG C, obtains activating pbo fiber;
Three, the hydroxy functionalized process of pbo fiber: 0.02g ~ 0.08g is activated pbo fiber and joins in 25ml ~ 100ml Lithium Aluminium Hydride-ether saturated solution, add hot reflux 0.5h ~ 2h under nitrogen protection, spend deionized water subsequently 1 time ~ 7 times, dry 10min ~ 60min at 80 DEG C ~ 150 DEG C, obtains hydroxy functionalized pbo fiber again;
Four, pbo fiber surface A PTMS grafting: the APTMS of 0.5ml ~ 2ml to be joined in 50ml ~ 150ml absolute ethyl alcohol and to mix, add the hydroxy functionalized pbo fiber of 0.02g ~ 0.08g subsequently, stir process 6h ~ 24h at 30 DEG C ~ 60 DEG C, then use absolute ethanol washing 1 time ~ 7 times, drying process obtains the pbo fiber of APTMS grafting;
Five, pbo fiber surface oxidation Graphene binary grafting: the graphene oxide of 0.05g ~ 0.15g functionalization is dissolved in 40ml ~ 100mlN; in dinethylformamide; and sonic oscillation 1h ~ 3h; add the pbo fiber of 0.02g ~ 0.08gAPTMS grafting subsequently; reflux heating 24h ~ 72h under nitrogen protection; use DMF washing the fibre 1 time ~ 7 times, after drying process, obtain binary graft modification pbo fiber.
2. the preparation method of a kind of binary graft modification pbo fiber according to claim 1, is characterized in that the decompression distillation described in step one carries out at the temperature of 40 DEG C ~ 70 DEG C.
3. the preparation method of a kind of binary graft modification pbo fiber according to claim 1, is characterized in that the sulfuric acid solution mass fraction described in step 2 is 20% ~ 80%.
4. the preparation method of a kind of binary graft modification pbo fiber according to claim 1, is characterized in that the speed that step 2 at room temperature stirs in stir process is 100r/min ~ 300r/min.
5. the preparation method of a kind of binary graft modification pbo fiber according to claim 1, is characterized in that the drying process described in step 4 is dry 10min ~ 60min at 50 DEG C ~ 100 DEG C.
6. the preparation method of a kind of binary graft modification pbo fiber according to claim 1, is characterized in that the drying process described in step 5 is dry 10min ~ 60min at 100 DEG C ~ 200 DEG C.
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| CN105645920B (en) * | 2016-01-13 | 2018-08-21 | 北京工业大学 | A method of improving aerogel composite bond strength |
| CN108486861B (en) * | 2018-04-25 | 2020-06-02 | 浙江梵彼斯特轻纺发展有限公司 | Preparation process of anti-ultraviolet aging PBO fiber |
| PE20212255A1 (en) * | 2018-11-26 | 2021-11-26 | Sceye Sa | PBO (Zylon®) FIBERS GRAFENED WITH GRAPHENE OXIDE; PRODUCTION METHOD AND APPLICATIONS IN AIRCRAFT HULL AND LIGHTER-THAN-AIR VEHICLES |
| CN112408904B (en) * | 2020-11-17 | 2022-06-14 | 上海群宝建材有限公司 | Concrete material with phase-change heat storage function and preparation method thereof |
| CN112626845B (en) * | 2020-12-18 | 2022-07-22 | 山东非金属材料研究所 | Surface modification method of PBO (poly (p-phenylene benzobisoxazole)) fibers |
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