CN101338038B - Method for enhancing fracture tensile strength of PBI/HP3O4 cast by sol-gel method - Google Patents

Method for enhancing fracture tensile strength of PBI/HP3O4 cast by sol-gel method Download PDF

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CN101338038B
CN101338038B CN2008100126979A CN200810012697A CN101338038B CN 101338038 B CN101338038 B CN 101338038B CN 2008100126979 A CN2008100126979 A CN 2008100126979A CN 200810012697 A CN200810012697 A CN 200810012697A CN 101338038 B CN101338038 B CN 101338038B
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pbi
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tensile strength
phosphoric acid
sol
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CN101338038A (en
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何荣桓
杨景帅
车全通
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Northeastern University China
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Abstract

A method for enhancing the breaking tensile strength of a PBI/H3PO4 film which is cast by a sol-gel method is characterized in that the powders of poly2, 2'-(metaphenylene)-5, 5'- bisbenzimidazole (PBI) are mixed with a phosphoric acid (H3PO4) solution, and is heated up to the temperature of 190 to 200 DEG C under the condition of nitrogen environment to form homogeneous reddish-brown PBI-H3PO4 sol; then the PBI-H3PO4 sol is dumped on a flat plate, and the high temperature sol is horizontally spread on the flat plate by a film blade to form high temperature PBI-H3PO4 sol film with 0.05 to 0.50mm thickness, the sol film is gelated into the film under the condition of freezing and then is prepared into phosphoric doped PBI film with enhanced breaking tensile strength, which satisfies a proton exchange film fuel cell for the requirements of acid doping level aspects of film electrolyte, by the phosphoric acid solution immerse method, the phosphoric acid solution heating treatment method or the organic solvent heating treatment method. The method of the invention has a short operating cycle and simple, convenient and feasible processing steps, and is easy to operate; the breaking tensile strength of the PBI-H3PO4 film being treated by enhancement is 6 to 16 MPa.

Description

Strengthen the PBI/H of sol-gel method casting 3PO 4The method of film fracture tensile strength
Technical field
The invention belongs to material science, particularly strengthen the PBI/H of sol-gel method casting 3PO 4The method of film fracture tensile strength.
Background technology
As the power technology of a kind of cleaning, efficient and stable performance, Proton Exchange Membrane Fuel Cells (PEMFC) has a good application prospect in fields such as development environmental type automobile, handheld devices.High temperature proton exchange film fuel cell (use temperature 80-180 ℃) can be simplified water, heat management system with it, improves advantage such as CO tolerance and becomes the research focus.Phosphoric acid (H 3PO 4) adulterated poly-2,2 '-(metaphenylene)-5,5 '-bisbenzimidazole (PBI) film is owing to its outstanding thermostability, good specific conductivity, lower methanol permeabilities etc. enjoy the investigator to pay close attention in development high temperature PEMFC, and are applied to the exploitation of fuel cell electric vehicle.The phosphate-doped PBI film of employings such as Wainright has been assembled direct methanol fuel cell (DMFC), is under the oxygenant condition at 200 ℃ of pure oxygens, and its output rating is 0.10W/cm 2For being the electrolytical hydrogen-oxygen (H of film with phosphate-doped PBI 150 ℃ of work 2/ O 2) PEMFC, maximum energy-density is 0.25W/cm 2, and battery operated 200 hours, do not observe the PBI film and degrade.According to another report, phosphate-doped PBI film can make H 150 ℃ the time 2/ O 2PEMFC moves more than the 5000h continuously.This shows phosphate-doped PBI film (PBI/H 3PO 4Film) all significant for development high temperature PEMFC and DMFC.
Poly-2,2 '-(metaphenylene)-5, the structural formula of 5 '-bisbenzimidazole (PBI) is:
Figure G2008100126979D00011
At present, adopt solution casting method to prepare the PBI mould material usually, soak phosphoric acid solution by the PBI film then and obtain phosphate-doped PBI film.N,N-dimethylacetamide (DMAc) is the most frequently used organic solvent of doing dissolving PBI powder.Yet because the rigid structure of PBI causes PBI to be difficult to dissolving, Xiao etc. adopts the polymeric solution direct pouring of PBI in PPA for this reason, utilizes airborne moisture to make polyphosphoric acid be hydrolyzed into ortho-phosphoric acid, has prepared phosphate-doped level at 20～40 PBI/H 3PO 4Film, and be applied to the film ionogen of PEMFC; Yet this method need not only be made troubles to operation with the polymeric solution while hot direct pouring film forming of PBI in PPA behind synthetic PBI, also makes the PBI that sticks on the reaction vessel inwall be difficult to utilization and cause waste.Jana etc. have reported PBI-H 3PO 4The heat reversible gel phenomenon of system points out that the PBI powder can be dissolved in dense H in the time of 180 ℃ 3PO 4The middle liquid colloidal sol that forms homogeneous, and have the phase transition process in the process of cooling, finally form solid gel.Based on above-mentioned theory, He Ronghuan etc. have developed and have utilized PBI-H 2O-H 3PO 4Ternary system prepares PBI/H 3PO 4The sol-gel method of film (number of patent application 200710012953.x), not only avoided the use of organic solvent in the film-forming process, solved the difficult problem that the PBI difficulty is dissolved in organic solvent, can also be by the PBI powder of the being convenient to standing storage sour adulterated film of casting, PBI is fully utilized, convenient and swift.Yet the film fracture tensile strength of this method casting awaits further improvement usually less than 3MPa.The phosphate-doped level of film (amount of substance of the phosphoric acid on every mol PBI repeating unit) is very big for the mechanical property influence of film.Litt etc. have studied the mechanical property of phosphate-doped PBI film under nitrogen atmosphere, discover when sour doped level in the PBI film near 2 the time, the power that film bore is better than the power that pure PBI film is born.Yet when sour doped level in the film surpassed 2, the mechanical property of film obviously descended with the increase of sour doped level.Under the room temperature condition, when the phosphate-doped level in the PBI film increased to 25.7 by 3.0, its fracture tensile strength dropped to 3.37MPa by 13.05MPa.Two imide nitrogen atoms in the PBI repeating unit combine with two phosphoric acid moleculeses in the hydrogen bond mode, and this bonding force is greater than the reactive force between the PBI skeleton, therefore when sour doped level in the film near 2 the time, the mechanical property of film is higher; And when the sour doped level of film surpassed 2, the too much phosphoric acid that combines with polymkeric substance in the hydrogen bond mode did not make PBI interchain molecular force reduce, and caused the mechanical property of film to descend.
Summary of the invention
The present invention is directed to PBI/H by the casting of PBI-phosphoric acid sol-gel method 3PO 4The problem that the film fracture tensile strength is lower provides a kind of PBI/H that strengthens the sol-gel method casting 3PO 4The method of film fracture tensile strength, and on the doped level of acid, satisfy as the electrolytical requirement of PEMFC film (sour doped level reaches 5～7).
Technical scheme of the present invention is:
1,, adopts sol-gel teeming practice (heat reversible gel technology), preparation high temperature PBI-H according to the described technology of 200710012953.x patent application 3PO 4Dissolved glue film:
PBI powder and phosphoric acid solution are mixed, add 8～17gPBI powder in the phosphoric acid solution of blending ratio by every 100mL85wt%, under inert atmosphere conditions, be heated to 190～200 ℃, form the sorrel PBI-H of homogeneous 3PO 4Colloidal sol is then with PBI-H 3PO 4Colloidal sol is poured on the flat board, makes PBI-H by knifing machine 3PO 4The colloidal sol level is sprawled on flat board, and forming thickness is the high temperature PBI-H of 0.05～0.50mm 3PO 4Dissolved glue film.
2, obtain sour doped level at 20～45 phosphate-doped PBI film by the cryogenic freezing gelation:
To be loaded with high temperature PBI-H 3PO 4The dull and stereotyped horizontal positioned of dissolved glue film, freezing 24～48h under-18 ± 3 ℃ of conditions, the PBI/H that freezing back is formed then 3PO 4Film and plate isolation.
3, be prepared into fracture tensile strength enhanced PBI/H by phosphoric acid solution soaking at room temperature method, phosphoric acid solution heat treated method or organic solvent heat treated method 3PO 4Film or pure PBI film, concrete steps are as follows:
3.1, phosphoric acid solution soaking at room temperature method:
(1) the preparation mass concentration is the phosphoric acid solution less than 75%.
(2) with the PBI/H after the freezing end 3PO 4Film is soaked in the phosphoric acid solution (or deionized water) of preparation fully, and 1～4h (being immersed in the deionized water needs more than the 24h) is soaked in sealing at ambient temperature under inert atmosphere conditions; Then with PBI/H 3PO 4Film (or PBI film) takes out, and with filter paper the acid and the water on film surface is removed.
(3) at PBI/H 3PO 4Before film (or PBI film) the dehydration distortion, with PBI/H 3PO 4Film (or PBI film) is open and flat to be fixed between two flat boards, to prevent PBI/H 3PO 4Film (or PBI film) distortion places baking oven (or vacuumize in baking oven, under 45 ± 5 ℃ of conditions) dry 8～12h under 85 ± 5 ℃ of conditions then; Then with PBI/H 3PO 4Film (or PBI film) places naturally cooling under the room temperature condition together with flat board, takes off flat board, obtains the PBI/H of the different sour doped level of fracture tensile strength enhanced 3PO 4Film (or pure PBI film) is preserved in sealing bag.
When wherein adopting deionized water to soak, obtain not having the adulterated pure PBI film of phosphoric acid.
3.2, phosphoric acid solution heat treated method:
(1) the preparation mass concentration is less than 75% phosphoric acid solution.
(2) with the PBI/H after the freezing end 3PO 4Film is soaked in the phosphoric acid solution (or deionized water) of preparation fully, and immersion is had PBI/H 3PO 4The phosphoric acid solution of film (or deionized water) reflux under inert atmosphere treats that solution boiling back keeps 10～15min; Adopt water-bath that reaction vessel is cooled to room temperature then, take out film, the acid and the water on film surface are removed with filter paper.
(3) at PBI/H 3PO 4Before film (or PBI film) the dehydration distortion, with PBI/H 3PO 4Film (or PBI film) is open and flat to be fixed between two flat boards, to prevent PBI/H 3PO 4Film (or PBI film) distortion places baking oven (or vacuumize in baking oven, under 45 ± 5 ℃ of conditions) dry 8～12h under 85 ± 5 ℃ of conditions then; Then with PBI/H 3PO 4Film (or PBI film) places naturally cooling under the room temperature condition together with flat board, takes off flat board, obtains the PBI/H of the different sour doped level of fracture tensile strength enhanced 3PO 4Film (or pure PBI film) is preserved in sealing bag.
When wherein adopting deionized water to carry out reflux, obtain not having the adulterated pure PBI film of phosphoric acid.
3.3, organic solvent heat treated method:
(1) with the PBI/H after the freezing end 3PO 4Film is soaked in the organic solvent fully, and wherein organic solvent is N,N-dimethylacetamide (DMAc), N-Methyl pyrrolidone (NMP) or dimethyl sulfoxide (DMSO) (DMSO); Immersion there is PBI/H 3PO 4The organic solvent of film is reflux under inert atmosphere, treats to keep 10～15min behind the organic solvent boiling; Adopt water-bath that reaction vessel is cooled to room temperature then, take out film, the organic solvent on film surface is removed with filter paper.
(2) at PBI/H 3PO 4Before the film distortion, with PBI/H 3PO 4Film is open and flat to be fixed between two flat boards, to prevent PBI/H 3PO 4Film distortion places baking oven (or vacuumize in baking oven, under 75 ± 5 ℃ of conditions) dry 8～12h under 115 ± 5 ℃ of conditions then; Then with PBI/H 3PO 4Symphysis places naturally cooling under the room temperature condition together with flat board, takes off flat board, obtains the PBI/H of the different sour doped level of fracture tensile strength enhanced 3PO 4Film is preserved in sealing bag.
PBI/H among the present invention 3PO 4When film was soaked in phosphoric acid solution, deionized water or organic solvent, the consumption of phosphoric acid solution, deionized water or organic solvent was with complete submergence PBI/H 3PO 4Film is as the criterion.
The PBI/H of the method for the invention preparation 3PO 4The sour doped level of film adopts the method for acid base titration quantitative, and calculation formula is as follows:
Figure G2008100126979D00041
In the formula, M: the concentration of standard NaOH solution, mol/L;
V: the volume of the standard NaOH solution that titration consumes, mL;
M:PBI/H 3PO 4Quality after the film oven dry, g;
The molecular weight of the every mol repeating unit of 308:PBI.
The PBI/H of the method for the invention preparation 3PO 4The mechanical property of film is characterized with fracture tensile strength and two indexs of elongation at break:
Fracture tensile strength (MPa)=maximum, force (N)/film initial cross sectional is amassed (mm 2)
Elongation at break (%)=(film fracture back leaf sight range-initial leaf sight range)/initial leaf sight range
The present invention adopts the sol-gel teeming practice to prepare high temperature PBI-H 3PO 4Behind the dissolved glue film, with PBI-H 3PO 4Dissolved glue film gelation under freezing conditions forms PBI/H 3PO 4Film is measured this PBI/H then 3PO 4The fracture tensile strength of film, and the PBI/H that forms with gelation at ambient temperature 3PO 4The fracture tensile strength of film compares, and the result shows the PBI/H that gelation under freezing conditions forms 3PO 4The film fracture tensile strength (see figure 2) that is significantly improved, the PBI/H that gelation under the freezing conditions is formed on this basis 3PO 4Film is further handled, and strengthens PBI/H 3PO 4The fracture tensile strength of film.
Dilute phosphoric acid immersion or heating method through same concentrations handled the PBI/H that obtains as can be seen from experiment 3PO 4The acid doped level, fracture tensile strength and elongation at break difference are little; And used phosphoric acid solution massfraction is low more, and the sour doped level of the PBI film that obtains is low more, and fracture tensile strength is big more.For example, handle the PBI/H that obtains through 40% phosphoric acid solution infusion method 3PO 4The sour doped level of film is 5.10, and fracture tensile strength is 10.97MPa; Handle the PBI/H that obtains through 40% phosphoric acid solution heating method 3PO 4The sour doped level of film is 5.00, and fracture tensile strength is 9.95MPa; Handle the PBI/H that obtains through 60% phosphoric acid solution infusion method 3PO 4The sour doped level of film is 6.77, and fracture tensile strength is 9.14MPa.From above example as can be seen, handle the PBI/H that obtains by above two kinds of methods 3PO 4Film has good fracture tensile strength, and also satisfies PEMFC for the requirement of ionogen on sour doped level.In addition, obtain pure PBI film (phosphate-doped level is zero) by deionized water heat treated method, its fracture tensile strength is 46.32MPa.
Compare the PBI/H that process organic solvent heat treated obtains with preceding two kinds of methods 3PO 4Film not only has higher fracture tensile strength (near 10MPa), and has higher elongation at break (about 130%), wherein the PBI/H through obtaining after the organic solvent DMAc heat treated 3PO 4The fracture tensile strength of film is that 12.14MPa and elongation at break are 131.14% (see figure 3); But handle the PBI/H that obtains through this method 3PO 4The sour doped level of film is all not high, all less than 3.
The phosphoric acid solution soaking at room temperature method that the inventive method is related, phosphoric acid solution heat treated method and organic solvent heat treated method, simple processing step are easily gone, easy handling.
Description of drawings
Fig. 1 is PBI/H in the fracture tensile strength testing experiment of the present invention 3PO 4The shape synoptic diagram of film (or PBI film).
Fig. 2 for room temperature condition of the present invention down with freezing conditions under gelation formation PBI/H 3PO 4The mechanical property comparison diagram of film, a are the PBI/H that gelation forms under the room temperature condition 3PO 4Film is tested the fracture tensile strength that obtains at ambient temperature, and b is the PBI/H that gelation forms under the freezing conditions 3PO 4Film is tested the fracture tensile strength that obtains at ambient temperature.Wherein X-coordinate is the mass content of PBI in unit volume phosphoric acid solution (massfraction 85%), and unit is the Grams Per Minute liter, and ordinate zou is PBI/H 3PO 4The fracture tensile strength of film; The PBI/H that the formed film of gelation forms than gelation under the room temperature condition under the freezing conditions as can be seen 3PO 4The fracture tensile strength height of film.
The PBI/H that Fig. 3 obtains after the organic solvent DMAc heat treated of the present invention for passing through of measuring down of room temperature condition of the present invention 3PO 4The mechanical property of film (curve a, sour doped level is 2.12) with do not adopt that organic solvent handles form PBI/H by gelation under the freezing conditions 3PO 4The mechanical property of film (curve b, sour doped level is 22.1) relatively improves by fracture tensile strength after the organic solvent heat treated as can be seen greatly.
Embodiment
The N,N-dimethylacetamide that the present invention adopts, N-Methyl pyrrolidone and dimethyl sulfoxide (DMSO) are analytical pure.
The raw material that the present invention prepares phosphoric acid solution is that mass concentration is 85% phosphoric acid solution, and purity is analytical pure, and water is deionized water.
The rare gas element that uses among the present invention is ordinary nitrogen.
The flat board that adopts in the invention process is the horizontal glass plate.
Vacuum operating of the invention process adopts SHZ-III type recirculated water vacuum pump (Shanghai Yarong Biochemical Instrument Plant).
The PBI powder that the present invention adopts is that its limiting viscosity is 0.82dL/g according to the PBI powder of the described method preparation of patent application 200710010916.5 (microwave is synthetic to gather 2,2 '-5, and 5 '-benzoglyoxaline reaches and gathers 2, the method for 5-benzoglyoxaline).
It below is the preferred embodiment of the present invention.
Embodiment 1
With PBI powder and mass concentration is that 85% phosphoric acid solution mixes, and blending ratio is heated to 200 ℃ by adding the 8gPBI powder in the phosphoric acid solution of every 100mL85wt% under the nitrogen atmosphere condition, form the sorrel PBI-H of homogeneous 3PO 4Colloidal sol is then with PBI-H 3PO 4Colloidal sol is poured on the flat board, makes high temperature PBI-H by knifing machine 3PO 4The colloidal sol level is sprawled on flat board, and forming thickness is the high temperature PBI-H of 0.05mm 3PO 4Dissolved glue film.
To be loaded with high temperature PBI-H 3PO 4The dull and stereotyped level of dissolved glue film is put into refrigerator, freezing 24h under-18 ± 3 ℃ of conditions, the PBI/H that freezing back is formed then 3PO 4Film and plate isolation.The preparation mass concentration is 20% phosphoric acid solution.With the PBI/H after the freezing end 3PO 4Film is soaked in the phosphoric acid solution of preparation fully, and sealing is at ambient temperature soaked 1h, solution and PBI/H under the feeding nitrogen atmosphere 3PO 4Acid balance in the film; Then with PBI/H 3PO 4Film takes out, and with filter paper the acid on film surface is removed.
At PBI/H 3PO 4Before the film distortion, with PBI/H 3PO 4Film is open and flat to be fixed between two flat boards, places baking oven dry 8h under 85 ± 5 ℃ of conditions; Then with PBI/H 3PO 4Symphysis places naturally cooling under the room temperature condition together with flat board, takes off flat board, the PBI/H that is enhanced 3PO 4Film is preserved in sealing bag.Adopting acid base titration to record sour doped level is 4.03.
Fracture tensile strength and elongation at break testing method are as follows: at first with PBI/H to be measured 3PO 4Film is made standard testing shape, PBI/H according to national standard with mould 3PO 4Film useful length 24mm, width 4mm as shown in Figure 1, utilizes Shenzhen newly to think carefully the CMT6502 of company microcomputer control electronics tension testing machine in atmospheric environment then, and room temperature condition is test PBI/H down 3PO 4The fracture tensile strength of film and elongation at break, rate of extension are 5mm/min; Recording fracture tensile strength is 16.23MPa, and elongation at break is 32.62%.
Will be with criticizing the high temperature PBI-H that the sol-gel teeming practice obtains 3PO 4Dissolved glue film is frozen into film in refrigerator and cooled, the PBI/H that obtains 3PO 4It is 11.93 that film adopts acid base titration to record sour doped level, and adopting and recording fracture tensile strength with quadrat method is 1.97MPa, and elongation at break is 101.10%.
Embodiment 2:
High temperature PBI-H 3PO 4The preparation method of dissolved glue film is with embodiment 1, and thickness is 0.10mm.
To be loaded with high temperature PBI-H 3PO 4The dull and stereotyped level of dissolved glue film is put into refrigerator, freezing 28h under-18 ± 3 ℃ of conditions, the PBI/H that freezing back is formed then 3PO 4Film and plate isolation.The preparation mass concentration is 40% phosphoric acid solution.With the PBI/H after the freezing end 3PO 4Film is soaked in the phosphoric acid solution of preparation fully, and sealing is at ambient temperature soaked 2h, solution and PBI/H under the feeding nitrogen atmosphere 3PO 4Acid balance in the film; Then with PBI/H 3PO 4Film takes out, and with filter paper the acid on film surface is removed.
At PBI/H 3PO 4Before the film distortion, with PBI/H 3PO 4Film is open and flat to be fixed between two flat boards, places baking oven dry 9h under 85 ± 5 ℃ of conditions; Then with PBI/H 3PO 4Symphysis places naturally cooling under the room temperature condition together with flat board, takes off flat board, the PBI/H that is enhanced 3PO 4Film is preserved in sealing bag.Adopting acid base titration to record sour doped level is 5.10.
Employing is with embodiment 1 described method, and recording fracture tensile strength is 10.97MPa, and elongation at break is 46.49%.
Embodiment 3:
High temperature PBI-H 3PO 4The preparation method of dissolved glue film is with embodiment 1, and thickness is 0.20mm.
To be loaded with high temperature PBI-H 3PO 4The dull and stereotyped level of dissolved glue film is put into refrigerator, freezing 36h under-18 ± 3 ℃ of conditions, the PBI/H that freezing back is formed then 3PO 4Film and plate isolation.The preparation mass concentration is 60% phosphoric acid solution.With the PBI/H after the freezing end 3PO 4Film is soaked in the phosphoric acid solution of preparation fully, and sealing is at ambient temperature soaked 3h, solution and PBI/H under the feeding nitrogen atmosphere 3PO 4Acid balance in the film; Then with PBI/H 3PO 4Film takes out, and with filter paper the acid on film surface is removed.
At PBI/H 3PO 4Before the film distortion, with PBI/H 3PO 4Film is open and flat to be fixed between two flat boards, places baking oven dry 10h under 85 ± 5 ℃ of conditions; Then with PBI/H 3PO 4Symphysis places naturally cooling under the room temperature condition together with flat board, takes off flat board, the PBI/H that is enhanced 3PO 4Film is preserved in sealing bag.Adopting acid base titration to record sour doped level is 6.77.
Employing is with embodiment 1 described method, and recording fracture tensile strength is 9.14MPa, and elongation at break is 47.89%.
Embodiment 4:
High temperature PBI-H 3PO 4The preparation method of dissolved glue film is with embodiment 1, and thickness is 0.50mm.
To be loaded with high temperature PBI-H 3PO 4The dull and stereotyped level of dissolved glue film is put into refrigerator, freezing 48h under-18 ± 3 ℃ of conditions, the PBI/H that freezing back is formed then 3PO 4Film and plate isolation.The preparation mass concentration is 75% phosphoric acid solution.With the PBI/H after the freezing end 3PO 4Film is soaked in the phosphoric acid solution of preparation fully, and sealing is at ambient temperature soaked 4h, solution and PBI/H under the feeding nitrogen atmosphere 3PO 4Acid balance in the film; Then with PBI/H 3PO 4Film takes out, and with filter paper the acid on film surface is removed.
At PBI/H 3PO 4Before the film distortion, with PBI/H 3PO 4Film is open and flat to be fixed between two flat boards, places baking oven, will vacuumize dry 12h under 45 ± 5 ℃ of conditions in the baking oven; Then with PBI/H 3PO 4Symphysis places naturally cooling under the room temperature condition together with flat board, takes off flat board, the PBI/H that is enhanced 3PO 4Film is preserved in sealing bag.Adopting acid base titration to record sour doped level is 7.43.
Employing is with embodiment 1 described method, and recording fracture tensile strength is 6.20MPa, and elongation at break is 56.93%.
Embodiment 5:
High temperature PBI-H 3PO 4The preparation method of dissolved glue film is with embodiment 1, and thickness is 0.40mm.
To be loaded with high temperature PBI-H 3PO 4The dull and stereotyped level of dissolved glue film is put into refrigerator, freezing 40h under-18 ± 3 ℃ of conditions, the PBI/H that freezing back is formed then 3PO 4Film and plate isolation.With the PBI/H after the freezing end 3PO 4Film is soaked in the deionized water fully, and sealing is at ambient temperature soaked 24h under the feeding nitrogen atmosphere; Then with PBI/H 3PO 4Film takes out, and with filter paper the water on film surface is removed, and obtains not having the adulterated pure PBI film of phosphoric acid.
Before PBI film distortion, be fixed between two flat boards the PBI film is open and flat, place baking oven, will vacuumize dry 12h under 45 ± 5 ℃ of conditions in the baking oven; Then the PBI symphysis is placed naturally cooling under the room temperature condition together with flat board, take off flat board, the PBI film that is enhanced is preserved in sealing bag.Adopting acid base titration to record sour doped level is 0.
Employing is with embodiment 1 described method, and recording fracture tensile strength is 37.33MPa, and elongation at break is 20.63%.
Embodiment 6:
With PBI powder and mass concentration is that 85% phosphoric acid solution mixes, and blending ratio is heated to 195 ℃ by adding the 12gPBI powder in the phosphoric acid solution of every 100mL85wt% under the nitrogen atmosphere condition, form the sorrel PBI-H of homogeneous 3PO 4Colloidal sol is then with PBI-H 3PO 4Colloidal sol is poured on the flat board, makes high temperature PBI-H by knifing machine 3PO 4The colloidal sol level is sprawled on flat board, and forming thickness is the high temperature PBI-H of 0.05mm 3PO 4Dissolved glue film.
To be loaded with high temperature PBI-H 3PO 4The dull and stereotyped level of dissolved glue film is put into refrigerator, freezing 24h under-18 ± 3 ℃ of conditions, the PBI/H that freezing back is formed then 3PO 4Film and plate isolation.The preparation mass concentration is 20% phosphoric acid solution.With the PBI/H after the freezing end 3PO 4Film is soaked in the phosphoric acid solution of preparation fully, and immersion is had PBI/H 3PO 4The phosphoric acid solution of film places reaction vessel, and this reaction vessel is placed in the oil bath, and reflux under nitrogen atmosphere treats that solution boiling back keeps 10min; With water-bath reaction vessel is cooled to room temperature then, takes out film, the acid on film surface is removed with filter paper.At PBI/H 3PO 4Before the film distortion, with PBI/H 3PO 4Film is open and flat to be fixed between two flat boards, places baking oven dry 8h under 85 ± 5 ℃ of conditions; Then with PBI/H 3PO 4Symphysis places naturally cooling under the room temperature condition together with flat board, takes off flat board, the PBI/H that is enhanced 3PO 4Film is preserved in sealing bag.Adopting acid base titration to record sour doped level is 2.98.
Employing is with embodiment 1 described method, and recording fracture tensile strength is 13.36MPa, and elongation at break is 32.68%.
Will be with criticizing the high temperature PBI-H that the sol-gel teeming practice obtains 3PO 4Dissolved glue film is frozen into film in refrigerator and cooled, the PBI/H that obtains 3PO 4It is 12.41 that film adopts acid base titration to record sour doped level, and adopting and recording fracture tensile strength with quadrat method is 2.39MPa, and elongation at break is 99.07%.
Embodiment 7:
High temperature PBI-H 3PO 4The preparation method of dissolved glue film is with embodiment 6, and thickness is 0.10mm.
To be loaded with high temperature PBI-H 3PO 4The dull and stereotyped level of dissolved glue film is put into refrigerator, freezing 28h under-18 ± 3 ℃ of conditions, the PBI/H that freezing back is formed then 3PO 4Film and plate isolation.The preparation mass concentration is 40% phosphoric acid solution.With the PBI/H after the freezing end 3PO 4Film is soaked in the phosphoric acid solution of preparation fully, and immersion is had PBI/H 3PO 4The phosphoric acid solution of film places reaction vessel, and this reaction vessel is placed in the oil bath, and reflux under nitrogen atmosphere treats that solution boiling back keeps 12min; With water-bath reaction vessel is cooled to room temperature then, takes out film, the acid on film surface is removed with filter paper.At PBI/H 3PO 4Before the film distortion, with PBI/H 3PO 4Film is open and flat to be fixed between two flat boards, places baking oven, will vacuumize dry 10h under 45 ± 5 ℃ of conditions in the baking oven; Then with PBI/H 3PO 4Symphysis places naturally cooling under the room temperature condition together with flat board, takes off flat board, the PBI/H that is enhanced 3PO 4Film is preserved in sealing bag.Adopting acid base titration to record sour doped level is 5.00.
Employing is with embodiment 1 described method, and recording fracture tensile strength is 9.95MPa, and elongation at break is 67.90%.
Embodiment 8:
High temperature PBI-H 3PO 4The preparation method of dissolved glue film is with embodiment 6, and thickness is 0.30mm.
To be loaded with high temperature PBI-H 3PO 4The dull and stereotyped level of dissolved glue film is put into refrigerator, freezing 36h under-18 ± 3 ℃ of conditions, the PBI/H that freezing back is formed then 3PO 4Film and plate isolation.The preparation mass concentration is 60% phosphoric acid solution.With the PBI/H after the freezing end 3PO 4Film is soaked in the phosphoric acid solution of preparation fully, and immersion is had PBI/H 3PO 4The phosphoric acid solution of film places reaction vessel, and this reaction vessel is placed in the oil bath, and reflux under nitrogen atmosphere treats that solution boiling back keeps 12min; With water-bath reaction vessel is cooled to room temperature then, takes out film, the acid on film surface is removed with filter paper.At PBI/H 3PO 4Before the film distortion, with PBI/H 3PO 4Film is open and flat to be fixed between two flat boards, places baking oven dry 11h under 85 ± 5 ℃ of conditions; Then with PBI/H 3PO 4Symphysis places naturally cooling under the room temperature condition together with flat board, takes off flat board, the PBI/H that is enhanced 3PO 4Film is preserved in sealing bag.Adopting acid base titration to record sour doped level is 7.00.
Employing is with embodiment 1 described method, and recording fracture tensile strength is 8.29MPa, and elongation at break is 52.59%.
Embodiment 9:
High temperature PBI-H 3PO 4The preparation method of dissolved glue film is with embodiment 6, and thickness is 0.50mm.
To be loaded with high temperature PBI-H 3PO 4The dull and stereotyped level of dissolved glue film is put into refrigerator, freezing 48h under-18 ± 3 ℃ of conditions, the PBI/H that freezing back is formed then 3PO 4Film and plate isolation.The preparation mass concentration is 75% phosphoric acid solution.With the PBI/H after the freezing end 3PO 4Film is soaked in the phosphoric acid solution of preparation fully, and immersion is had PBI/H 3PO 4The phosphoric acid solution of film places reaction vessel, and this reaction vessel is placed in the oil bath, and reflux under nitrogen atmosphere treats that solution boiling back keeps 15min; With water-bath reaction vessel is cooled to room temperature then, takes out film, the acid on film surface is removed with filter paper.At PBI/H 3PO 4Before the film distortion, with PBI/H 3PO 4Film is open and flat to be fixed between two flat boards, places baking oven, will vacuumize dry 12h under 45 ± 5 ℃ of conditions in the baking oven; Then with PBI/H 3PO 4Symphysis places naturally cooling under the room temperature condition together with flat board, takes off flat board, the PBI/H that is enhanced 3PO 4Film is preserved in sealing bag.Adopting acid base titration to record sour doped level is 7.60.
Employing is with embodiment 1 described method, and recording fracture tensile strength is 7.35MPa, and elongation at break is 70.21%.
Embodiment 10:
High temperature PBI-H 3PO 4The preparation method of dissolved glue film is with embodiment 6, and thickness is 0.40mm.
To be loaded with high temperature PBI-H 3PO 4The dull and stereotyped level of dissolved glue film is put into refrigerator, freezing 40h under-18 ± 3 ℃ of conditions, the PBI/H that freezing back is formed then 3PO 4Film and plate isolation.With the PBI/H after the freezing end 3PO 4Film is soaked in the deionized water fully, and immersion is had PBI/H 3PO 4The deionized water of film places reaction vessel, and this reaction vessel is placed in the oil bath, and reflux under nitrogen atmosphere treats that solution boiling back keeps 15min; With water-bath reaction vessel is cooled to room temperature then, takes out film, the acid on film surface is removed, obtain not having the adulterated pure PBI film of phosphoric acid with filter paper.Before PBI film distortion, be fixed between two flat boards the PBI film is open and flat, place baking oven, will vacuumize dry 12h under 45 ± 5 ℃ of conditions in the baking oven; Then the PBI symphysis is placed naturally cooling under the room temperature condition together with flat board, take off flat board, the PBI film that is enhanced is preserved in sealing bag.Adopting acid base titration to record sour doped level is 0.
Employing is with embodiment 1 described method, and recording fracture tensile strength is 46.32MPa, and elongation at break is 24.86%.
Embodiment 11:
With PBI powder and mass concentration is that 85% phosphoric acid solution mixes, and blending ratio is heated to 190 ℃ by adding the 17gPBI powder in the phosphoric acid solution of every 100mL85wt% under the nitrogen atmosphere condition, form the sorrel PBI-H of homogeneous 3PO 4Colloidal sol is then with PBI-H 3PO 4Colloidal sol is poured on the flat board, makes high temperature PBI-H by knifing machine 3PO 4The colloidal sol level is sprawled on flat board, and forming thickness is the high temperature PBI-H of 0.50mm 3PO 4Dissolved glue film.
To be loaded with high temperature PBI-H 3PO 4The dull and stereotyped level of dissolved glue film is put into refrigerator, freezing 48h under-18 ± 3 ℃ of conditions, the PBI/H that freezing back is formed then 3PO 4Film and plate isolation.
With the PBI/H after the freezing end 3PO 4Film is soaked in the N,N-dimethylacetamide fully, and immersion is had PBI/H 3PO 4The N,N-dimethylacetamide of film places reaction vessel, and this reaction vessel is placed in the oil bath, and reflux under nitrogen atmosphere treats that N,N-dimethylacetamide boiling back keeps 15min; With water-bath reaction vessel is cooled to room temperature then, takes out film, the N,N-dimethylacetamide on film surface is removed with filter paper.At PBI/H 3PO 4Before the film distortion, with PBI/H 3PO 4Film is open and flat to be fixed between two flat boards, places baking oven dry 8h under 115 ± 5 ℃ of conditions; Then with PBI/H 3PO 4Symphysis places naturally cooling under the room temperature condition together with flat board, takes off flat board, the PBI/H that is enhanced 3PO 4Film is preserved in sealing bag.Adopting acid base titration to record sour doped level is 2.12.
Employing is with embodiment 1 described method, and recording fracture tensile strength is 12.14MPa, and elongation at break is 131.14%.
Will be with criticizing the high temperature PBI-H that the sol-gel teeming practice obtains 3PO 4Dissolved glue film is frozen into film in refrigerator and cooled, the PBI/H that obtains 3PO 4It is 25.22 that film adopts acid base titration to record sour doped level, and adopting and recording fracture tensile strength with quadrat method is 2.03MPa, and elongation at break is 125.41%.
Embodiment 12:
High temperature PBI-H 3PO 4The preparation method of dissolved glue film is with embodiment 11, and thickness is 0.30mm.
To be loaded with high temperature PBI-H 3PO 4The dull and stereotyped level of dissolved glue film is put into refrigerator, freezing 36h under-18 ± 3 ℃ of conditions, the PBI/H that freezing back is formed then 3PO 4Film and plate isolation.
With the PBI/H after the freezing end 3PO 4Film is soaked in the N-Methyl pyrrolidone fully, and immersion is had PBI/H 3PO 4The N-Methyl pyrrolidone of film places reaction vessel, and this reaction vessel is placed in the oil bath, and reflux under nitrogen atmosphere treats that N-Methyl pyrrolidone boiling back keeps 12min; With water-bath reaction vessel is cooled to room temperature then, takes out film, the N-Methyl pyrrolidone on film surface is removed with filter paper.At PBI/H 3PO 4Before the film distortion, with PBI/H 3PO 4Film is open and flat to be fixed between two flat boards, places baking oven dry 10h under 115 ± 5 ℃ of conditions; Then with PBI/H 3PO 4Symphysis places naturally cooling under the room temperature condition together with flat board, takes off flat board, the PBI/H that is enhanced 3PO 4Film is preserved in sealing bag.Adopting acid base titration to record sour doped level is 0.74.
Employing is with embodiment 1 described method, and recording fracture tensile strength is 6.95MPa, and elongation at break is 130.05%.
Embodiment 13:
High temperature PBI-H 3PO 4The preparation method of dissolved glue film is with embodiment 11, and thickness is 0.05mm.
To be loaded with high temperature PBI-H 3PO 4The dull and stereotyped level of dissolved glue film is put into refrigerator, freezing 24h under-18 ± 3 ℃ of conditions, the PBI/H that freezing back is formed then 3PO 4Film and plate isolation.
With the PBI/H after the freezing end 3PO 4Film is soaked in the dimethyl sulfoxide (DMSO) fully, and immersion is had PBI/H 3PO 4The dimethyl sulfoxide (DMSO) of film places reaction vessel, and this reaction vessel is placed in the oil bath, and reflux under nitrogen atmosphere treats that dimethyl sulfoxide (DMSO) boiling back keeps 10min; With water-bath reaction vessel is cooled to room temperature then, takes out film, the dimethyl sulfoxide (DMSO) on film surface is removed with filter paper.At PBI/H 3PO 4Before the film distortion, with PBI/H 3PO 4Film is open and flat to be fixed between two flat boards, places baking oven, will vacuumize dry 12h under 75 ± 5 ℃ of conditions in the baking oven; Then with PBI/H 3PO 4Symphysis places naturally cooling under the room temperature condition together with flat board, takes off flat board, the PBI/H that is enhanced 3PO 4Film is preserved in sealing bag.Adopting acid base titration to record sour doped level is 0.60.
Employing is with embodiment 1 described method, and recording fracture tensile strength is 9.74MPa, and elongation at break is 84.47%.

Claims (9)

1. one kind strengthens the PBI/H that sol-gel method is cast 3PO 4The method of film fracture tensile strength is characterized in that comprising the steps:
(1) PBI powder and phosphoric acid solution are mixed, add 8～17gPBI powder in the phosphoric acid solution of blending ratio by every 100mL85wt%, under inert atmosphere conditions, be heated to 190～200 ℃, form the sorrel PBI-H of homogeneous 3PO 4Colloidal sol is then with PBI-H 3PO 4Colloidal sol is poured on the flat board, makes high temperature PBI-H by knifing machine 3PO 4The colloidal sol level is sprawled on flat board, and forming thickness is the high temperature PBI-H of 0.05～0.5mm 3PO 4Dissolved glue film;
(2) will be loaded with high temperature PBI-H 3PO 4The dull and stereotyped level of dissolved glue film places freezing 24～48h under-18 ± 3 ℃ of conditions, then the PBI/H that freezing back is formed 3PO 4Film and plate isolation;
(3) obtain the PBI/H of the different sour doped level of fracture tensile strength enhanced by phosphoric acid solution soaking at room temperature method, phosphoric acid solution heat treated method or organic solvent heat treated method 3PO 4Film is preserved in sealing bag.
2. a kind of PBI/H that strengthens the sol-gel method casting according to claim 1 3PO 4The method of film fracture tensile strength is characterized in that described phosphoric acid solution soaking at room temperature method step is:
(1) with the PBI/H after the freezing end 3PO 4Film is soaked in the phosphoric acid solution, and the room temperature condition lower seal soaks 1～4h under inert atmosphere conditions; Then with PBI/H 3PO 4Film takes out, and with filter paper the acid on film surface is removed;
(2) with PBI/H 3PO 4Film is open and flat to be fixed between two flat boards, places baking oven dry 8～12h under 85 ± 5 ℃ of conditions, or places baking oven, will vacuumize dry 8～12h under 45 ± 5 ℃ of conditions in the baking oven; Then with PBI/H 3PO 4Symphysis places naturally cooling under the room temperature condition together with flat board, takes off flat board, obtains the PBI/H of the different sour doped level of fracture tensile strength enhanced 3PO 4Film is preserved in sealing bag.
3. a kind of PBI/H that strengthens the sol-gel method casting according to claim 1 3PO 4The method of film fracture tensile strength is characterized in that described phosphoric acid solution heat treated method step is:
(1) with the PBI/H after the freezing end 3PO 4Film is soaked in phosphoric acid solution, and immersion is had PBI/H 3PO 4The phosphoric acid solution of film is reflux under inert atmosphere, treats that solution boiling back keeps 10～15min; Be cooled to room temperature then, take out film, the acid on film surface is removed with filter paper;
(2) with PBI/H 3PO 4Film is open and flat to be fixed between two flat boards, places baking oven dry 8～12h under 85 ± 5 ℃ of conditions, or places baking oven, will vacuumize dry 8～12h under 45 ± 5 ℃ of conditions in the baking oven; Then with PBI/H 3PO 4Symphysis places naturally cooling under the room temperature condition together with flat board, takes off flat board, obtains the PBI/H of the different sour doped level of fracture tensile strength enhanced 3PO 4Film is preserved in sealing bag.
4. a kind of PBI/H that strengthens the sol-gel method casting according to claim 1 3PO 4The method of film fracture tensile strength is characterized in that described organic solvent heat treated method step is:
(1) with the PBI/H after the freezing end 3PO 4Film is soaked in the organic solvent fully; Immersion there is PBI/H 3PO 4The organic solvent of film is reflux under inert atmosphere, treats to keep 10～15min behind the organic solvent boiling; Be cooled to room temperature then, take out film, the organic solvent on film surface is removed with filter paper;
(2) with PBI/H 3PO 4Film is open and flat to be fixed between two flat boards, places baking oven dry 8～12h under 115 ± 5 ℃ of conditions, or places baking oven, will vacuumize dry 8～12h under 75 ± 5 ℃ of conditions in the baking oven; Then with PBI/H 3PO 4Symphysis places naturally cooling under the room temperature condition together with flat board, takes off flat board, obtains the PBI/H of the different sour doped level of fracture tensile strength enhanced 3PO 4Film is preserved in sealing bag.
5. according to claim 2 or 3 described a kind of PBI/H that strengthen the sol-gel method casting 3PO 4The method of film fracture tensile strength is characterized in that described phosphoric acid solution mass concentration is the phosphoric acid solution less than 75%; The consumption of described phosphoric acid solution is with complete submergence PBI/H 3PO 4Film is as the criterion.
6. according to claim 2,3 or 4 described a kind of PBI/H that strengthen the sol-gel method casting 3PO 4The method of film fracture tensile strength is characterized in that at PBI/H 3PO 4Before the film distortion, with PBI/H 3PO 4Film is open and flat to be fixed between two flat boards.
7. according to claim 2,3 or 4 described a kind of PBI/H that strengthen the sol-gel method casting 3PO 4The method of film fracture tensile strength, it is characterized in that described oven dry finish after with PBI/H 3PO 4Symphysis together is placed on the room temperature condition naturally cooling with flat board, can not take off dull and stereotyped to prevent the film distortion after oven dry immediately.
8. a kind of PBI/H that strengthens the sol-gel method casting according to claim 4 3PO 4The method of film fracture tensile strength is characterized in that described organic solvent is a N,N-dimethylacetamide, N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO), and the consumption of organic solvent is with complete submergence PBI/H 3PO 4Film is as the criterion.
9. according to claim 3 or 4 described a kind of PBI/H that strengthen the sol-gel method casting 3PO 4The method of film fracture tensile strength is characterized in that described heating finishes the back and adopts water-bath that reaction vessel is cooled to room temperature.
CN2008100126979A 2008-08-07 2008-08-07 Method for enhancing fracture tensile strength of PBI/HP3O4 cast by sol-gel method Expired - Fee Related CN101338038B (en)

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