CN102660043A - Preparation of novel polyphosphazene alkaline membrane - Google Patents

Preparation of novel polyphosphazene alkaline membrane Download PDF

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CN102660043A
CN102660043A CN2012101446006A CN201210144600A CN102660043A CN 102660043 A CN102660043 A CN 102660043A CN 2012101446006 A CN2012101446006 A CN 2012101446006A CN 201210144600 A CN201210144600 A CN 201210144600A CN 102660043 A CN102660043 A CN 102660043A
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poly phosphazene
film
preparation
quaternary
alkalescence
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汪中明
张婷
韩克飞
朱红
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Beijing University of Chemical Technology
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Abstract

The invention provides a preparation method of a novel polyphosphazene alkaline membrane for a fuel cell. The preparation method of the polyphosphazene alkaline membrane comprises the following steps of: performing a quaternary phosphatization reaction on polyphosphazene loaded with benzyl bromide or alkyl bromide at the tail end of a branch chain and a quaternary phosphatization reagent to obtain quaternary phosphatization polyphosphazene; dissolving into an organic solvent, and performing curtain coating and membrane forming; and soaking with an alkaline liquor, wherein triaryl phosphine or trialkyl phosphine can be taken as the quaternary phosphatization reagent. A preparation method of a polyphosphazene crosslinked alkaline membrane comprises the following steps of: doping a crosslinking agent into the quaternary phosphatization reagent; reacting with polyphosphazene loaded with benzyl bromide or alkyl bromide at the tail end of a branch chain to obtain crosslinked quaternary phosphatization polyphosphazene; dissolving into an organic solvent, and performing curtain coating and membrane forming; and soaking with an alkaline liquor, wherein the crosslinking agent can be a polyethylene glycol sodium salt or diamine. A preparation method of a polyphosphazene coblended alkaline membrane comprises the following steps of: doping a polyalcohol into quaternary phosphatization polyphosphazene; performing curtain coating and membrane forming; and soaking with an alkaline liquor, wherein the polyalcohol can be polyethylene glycol or polyvinyl alcohol.

Description

The preparation of novel poly phosphazene alkalescence film
Technical field
The invention belongs to the preparation field of fuel cell, be specifically related to the preparation of novel poly phosphazene alkalescence film, the crosslinked alkaline film of poly phosphazene and poly phosphazene blend alkalescence film with alkaline film.
Background technology
Fuel cell (Fuel cells) is the power generation assembly that the chemical energy of fuel is directly changed into electric energy through the mode of electrochemical reaction; It is a kind of energy conversion device of cleaning; Expectation replacement present stage traditional energy and rechargeable lithium ion batteries are considered to promising chemical power source of 21 century.With alkaline film hydrogen-oxygen fuel cell is example, and the electrochemical reaction of its principle of work and generation is following, anode: 2H 2+ 4OH -→ 4H 2O+4e -Negative electrode: O 2+ 2H 2O+4e -→ 4OH -Total cell reaction: 2H 2+ O 2→ 2H 2O+ electric energy+heat, OH -Be transmitted to anode through alkaline film from negative electrode and participate in electrode reaction, also play a part simultaneously to intercept fuel, this shows that polymer dielectric film is a key part of fuel cell, its performance quality directly affects fuel cell performance.What generally adopt at present is the PEM that under acidic conditions, uses.Typical PEM is the Nafion film that du pont company is produced, and it has excellent heat, chemicalstability, and proton conductivity is high.Yet also there are some shortcomings in the Nafion film, such as: the kinetic reaction of electrode is slow in the sour environment, and electrode catalyst adopts noble metal platinum, and it is higher to cause it to be used for the fuel cell cost, has hindered industrialization process.
Recently, research focuses on the alkaline film that is used for alkaline medium.The alkaline fuel cell service temperature is low, and control more easily is than in sour environment, there being the reaction of higher electrode kinetics to make higher (the G é raldine Merle et al.Journal of Membrane Science of voltage; 2011,377:1-35), at present; What reported is carrier with the polymkeric substance, through its functionalization, comprises chloromethylation or bromination, quaternized Huo quaternary phosphineization, quaternization; Or with the small molecules copolymerization that has quaternary ammonium group; Make have on the main polymer chain can carry out hydroxide ion conduction quaternary ammonium Huo quaternary phosphine group as alkaline film, have good heat, chemicalstability, ionic conductance is 1～10 2MS cm -1Scope meets the requirement of present stage alkalescence film.With the polyarylsulphone chloromethylation, tertiary amineization, quaternized, film forming step obtain high ion exchange volume and heat, chemicalstability is high, good mechanical property, the high alkaline film of specific conductivity under the high-temperature alkaline condition like: Zhuan Lin etc. (Zhuan Lin etc., CN 101862608 A); Yan Yushan etc. (Yan Yushan et al.Angew.Chem.Int.Ed., 2009,48:6499-6502) through the chloromethylation ， quaternary phosphineization to polysulfones, alkalinization step has obtained the strong alkaline film of a kind of alkalescence, and its ionic conductance reaches 27mS cm in the time of 20 ℃ -1, heat, alkali, permanent stability are all better, are expected to be used for alkaline fuel cell.Fang Jun etc. (Fang Jun etc., CN 102206386 A) use unsaturated hydrocarbons that contains glyoxaline cation and the aromatic hydrocarbons that contains unsaturated double-bond or ester through the free-radical polymerized alkaline film that contains imidazole cation group that synthesized, and under high alkali environment, still have good ionic conduction.
The poly phosphazene high polymer main chain is by nitrogen phosphorus key Dan Shuanjian alternately, on the main chain phosphorus atom, is connected with two side-chain radicals.Because its main chain has good kindliness, the such special construction of whole poly phosphazene polymer makes it possess good thermostability, oxidation-resistance, premium propertiess such as water-fast, chemicals-resistant, radiation hardness, high-low temperature resistant.Poly phosphazene not only self has superiority, and it and other materials are nano combined, and synthetic through functionalization makes it in a lot of fields as biomedical; Store energy, all there is application aspects such as solid state electrolyte, especially aspect electrochemistry, important application are arranged; Allcock, Wycisk, Pintauro etc. are through the sulfonated or phosphorylation (H.R.Allcock of poly phosphazene; Macromolecules, 2002,35:3484-3489; R.Wycisk et.al, Adv Polym Sci, 2008,216:157-183), be used for all having carried out a large amount of research explorations aspect the PEM at poly phosphazene.
Based on the progress of present alkaline film and the premium properties of poly phosphazene; The poly phosphazene that this paper chooses side chain end load bromotoluene or alkyl bromide is a basic framework, through quaternary phosphineization, is dissolved in the organic solvent casting film-forming successively; Alkalinization step, preparation poly phosphazene alkalescence film; Mix oxygen containing polymkeric substance sodium salt or diamines in the Zai quaternary phosphine reagent, the crosslinked alkaline film of preparation poly phosphazene; Mix oxygen containing polyalcohols in the Zai quaternary phosphine poly phosphazene organic solution, preparation poly phosphazene blend alkalescence film.
Summary of the invention
The purpose of this invention is to provide the preparation method of fuel cell with novel poly phosphazene alkalescence film.Prepared alkaline film can use the casting method film forming, and institute's film forming is more transparent, and ionic conductance is preferably arranged, and heat, mechanical stability is good.
A kind of poly phosphazene alkalescence film of the present invention is characterized in that, through the bromo poly phosphazene Yu quaternary phosphine reagent carries out the quaternary phosphine reaction; Obtain the quaternary phosphine poly phosphazene; It is dissolved in the organic solution that obtains the quaternary phosphine poly phosphazene behind the organic solvent, behind its casting film-forming, uses 1mol L again -1The KOH solution soaking promptly obtains poly phosphazene alkalescence film.
Bromo poly phosphazene of the present invention can be the poly phosphazene of side chain end load bromotoluene or alkyl bromide.
Quaternary phosphine reagent A of the present invention can be selected for use as shown in the formula 1 structure:
Figure BSA00000715277100021
Formula 1 quaternary phosphine reagent A
L 1Can be
Figure BSA00000715277100022
C mH 2m+1, L 2Can be
Figure BSA00000715277100023
C mH 2m+1, L 3Can be C mH 2m+1, n=1～8 wherein, m=1～10 ， quaternary phosphine reagent A can be L 1, L 2, L 3Between permutation and combination arbitrarily.
The organic solvent of solubilized quaternary phosphine poly phosphazene of the present invention can be N, the mixed solvent of one or more of dinethylformamide, DMSO 99.8MIN., DMAC N,N, N-Methyl pyrrolidone.
The crosslinked alkaline film of a kind of poly phosphazene of the present invention is characterized in that, after in above-mentioned quaternary phosphine reagent A, mixing linking agent Ji quaternary phosphine reagent A and linking agent mixing, reacts with the bromo poly phosphazene, obtains crosslinked quaternary phosphine poly phosphazene; After it is dissolved in the organic solvent casting film-forming, use 1mol L again -1The KOH solution soaking promptly obtains the crosslinked alkaline film of poly phosphazene.
Linking agent wherein can be B, C, D or the E as shown in the formula 2～5:
Figure BSA00000715277100025
(relative molecular mass is in 60～6000 scopes)
The structural formula of formula 2B
Figure BSA00000715277100031
(wherein X can be C, N, O, S)
The structural formula of formula 3C
Figure BSA00000715277100032
(Y wherein can be C, N, q=1～10)
The structural formula of formula 4D
Figure BSA00000715277100033
(r＝2～5)
The structural formula of formula 5E
A kind of poly phosphazene blend alkalescence film of the present invention is characterized in that, mixes polyalcohols in the organic solution of described quaternary phosphine poly phosphazene, promptly mix the organic solution casting film-forming of polyalcohols De quaternary phosphine poly phosphazene after, use 1mol L again -1The KOH solution soaking promptly obtains poly phosphazene blend alkalescence film.Polyalcohols wherein can be F or the G as shown in the formula 6,7:
Figure BSA00000715277100034
(relative molecular mass is in 2.5～300,000 scopes)
The structural formula of formula 6F
(relative molecular mass is in 60～6000 scopes)
The structural formula of formula 7G
The practical implementation step is following:
1, poly phosphazene alkalescence film:
1) poly phosphazene of getting a certain amount of load bromotoluene or alkyl bromide structural unit is dissolved in the tetrahydrofuran solution, drips the tetrahydrofuran solution of a certain amount of quaternary phosphine reagent A, stirs certain hour at a certain temperature, obtains quaternary phosphine poly phosphazene deposition.
2) Ci quaternary phosphine poly phosphazene is dissolved in a certain amount of organic solvent; The preferred N of solvent; The mixed solvent of one or more of dinethylformamide, DMSO 99.8MIN., DMAC N,N, N-Methyl pyrrolidone, casting film-forming certain hour under the certain temperature.After film taken off, be soaked in 1mol L -1Carry out the IX certain hour in the KOH solution, behind the deionized water rinsing, promptly obtain poly phosphazene alkalescence film.
2, the crosslinked alkaline film of poly phosphazene:
1) oxygen-containing polymers is dissolved in the THF that dewaters, at N 2Under add sodium hydride reaction, obtain the tetrahydrofuran solution of oxygen-containing polymers sodium salt B.
Mix linking agent in the 2) Zai quaternary phosphine reagent A; Promptly prepare one or more mixing among quaternary phosphine reagent A, oxygen-containing polymers sodium salt B, two amine linking agent C, D, the E; Be dissolved in THF by the certain mass proportioning; Be added dropwise in the tetrahydrofuran solution of poly phosphazene of side chain end load bromotoluene or alkyl bromide, stir certain hour under the certain temperature, obtain crosslinked quaternary phosphine poly phosphazene deposition.
3) this crosslinked quaternary phosphine poly phosphazene deposition is dissolved in the certain amount of organic solvent; The preferred N of solvent; The mixed solvent of one or more of dinethylformamide, DMSO 99.8MIN., DMAC N,N, N-Methyl pyrrolidone, casting film-forming certain hour under the certain temperature.After film taken off, be soaked in 1mol L -1Carry out the IX certain hour in the KOH solution, behind the deionized water rinsing, promptly obtain the crosslinked alkaline film of poly phosphazene.
3, poly phosphazene blend alkalescence film:
In the organic solution of quaternary phosphine poly phosphazene described in the membrane prepare of poly phosphazene alkalescence, mix blend reagent; Promptly in the quaternary phosphine poly phosphazene organic solution that obtains, mix the polyalcohols F of certain mass, one or both mixing among the G, casting film-forming certain hour under the certain temperature.After film taken off, be soaked in 1mol L -1Carry out the IX certain hour in the KOH solution, behind the deionized water rinsing, promptly obtain poly phosphazene blend alkalescence film.
The present invention compares with said background technology, and the prepared alkaline film of the present invention possesses mechanical property preferably, and thermo-chemical stability is good, also has ionic conduction performance preferably, meets the requirement of present stage fuel cell alkalescence film.
Embodiment
Through embodiment the present invention is detailed below, but is not limitation of the present invention.
Embodiment 1
Gather preparation to methylphenoxy phosphine nitrile alkalescence film
1) quaternary phosphineization is gathered the preparation to methylphenoxy phosphine nitrile film
In the 0.5g bromo gathers the 20mL tetrahydrofuran solution of methylphenoxy phosphine nitrile, drip the 20mL tetrahydrofuran solution of excessive triphenylphosphine, under 10～90 ℃, stir 1～7h, obtain light-yellow precipitate and be quaternary phosphineization and gather methylphenoxy phosphine nitrile.It is dissolved in the N of 5mL, and dinethylformamide solution is after the ultrasonic dissolution de-bubble, in 20～120 ℃ of curtain coating 12～60h film forming.
2) gather preparation to methylphenoxy phosphine nitrile alkalescence film
Above-mentioned quaternary phosphineization is gathered methylphenoxy phosphine nitrile film at 1mol L -1Soak 48h in the KOH solution and carry out IX, obtain light yellow film after washing with deionized water again and be and gather methylphenoxy phosphine nitrile alkalescence film.
Embodiment 2
Gather preparation to the crosslinked alkaline film of methylphenoxy phosphine nitrile
1) quaternary phosphineization is gathered the preparation to methylphenoxy phosphine nitrile cross linking membrane
, the 0.5g bromo drips the triphenylphosphine of certain mass proportioning and the 30mL tetrahydrofuran solution of polyoxyethylene glycol (200) sodium in gathering the 20mL tetrahydrofuran solution of methylphenoxy phosphine nitrile; Under 10～90 ℃; Stir 1～7h, obtain light-yellow precipitate and be crosslinked De quaternary phosphineization and gather methylphenoxy phosphine nitrile.It is dissolved in the N of 5mL, and dinethylformamide solution is after the ultrasonic dissolution de-bubble, in 20～120 ℃ of curtain coating 12～60h film forming.
2) gather preparation to the crosslinked alkaline film of methylphenoxy phosphine nitrile
Above-mentioned quaternary phosphineization is gathered methylphenoxy phosphine nitrile cross linking membrane at 1mol L -1Soak 48h in the KOH solution and carry out IX, obtain light yellow film after washing with deionized water again and be and gather the crosslinked alkaline film of methylphenoxy phosphine nitrile.
Embodiment 3
Gather preparation to methylphenoxy phosphine nitrile blend alkalescence film
1) quaternary phosphineization is gathered the preparation to methylphenoxy phosphine nitrile blend film
In the 0.5g bromo gathers the 20mL tetrahydrofuran solution of methylphenoxy phosphine nitrile, drip the 20mL tetrahydrofuran solution of excessive triphenylphosphine, under 10～90 ℃, stir 1～7h, obtain light-yellow precipitate and be quaternary phosphineization and gather methylphenoxy phosphine nitrile.It is dissolved in the N of 5mL, and dinethylformamide solution is added dropwise to a certain amount of polyoxyethylene glycol (200), after the ultrasonic dissolution de-bubble, in 20～120 ℃ of curtain coating 12～60h film forming.
2) gather preparation to methylphenoxy phosphine nitrile blend alkalescence film
Above-mentioned quaternary phosphineization is gathered methylphenoxy phosphine nitrile blend film at 1mol L -1Soak 48h in the KOH solution and carry out IX, obtain light yellow film after washing with deionized water again and be and gather methylphenoxy phosphine nitrile blend alkalescence film.
The preparation of other poly phosphazene alkalescence films and the crosslinked alkaline film of poly phosphazene, poly phosphazene blend alkalescence film can be with reference to above embodiment.

Claims (8)

1. a fuel cell is with the preparation of poly phosphazene alkalescence film; It is characterized in that, Yu quaternary phosphine reagent carries out the quaternary phosphine reaction, obtain the quaternary phosphine poly phosphazene through the bromo poly phosphazene; Be dissolved in the organic solution that obtains the quaternary phosphine poly phosphazene behind the organic solvent; Behind its casting film-forming, use the KOH solution soaking again, promptly obtain poly phosphazene alkalescence film.
2. the preparation of poly phosphazene alkalescence film as claimed in claim 1 is characterized in that described bromo poly phosphazene is the poly phosphazene of side chain end load bromotoluene or alkyl bromide.
3. the preparation of poly phosphazene alkalescence film as claimed in claim 1 is characterized in that described quaternary phosphine reagent can be selected trialkyl phosphine or triaryl phosphine for use:
Figure FSA00000715277000011
L wherein 1Can be
Figure FSA00000715277000012
C mH 2m+1, L 2Can be
Figure FSA00000715277000013
Figure FSA00000715277000014
C mH 2m+1, L 3Can be C mH 2m+1(n=1～8, m=1～10) ， quaternary phosphine reagent can be L 1, L 2, L 3Between permutation and combination arbitrarily.
4. the preparation of poly phosphazene alkalescence film as claimed in claim 1; It is characterized in that; The organic solvent of described solubilized quaternary phosphine poly phosphazene can be N, the mixed solvent of one or more of dinethylformamide, DMSO 99.8MIN., DMAC N,N, N-Methyl pyrrolidone.
5. the preparation of the crosslinked alkaline film of poly phosphazene; It is characterized in that, described quaternary phosphine reagent of claim 1 and linking agent are mixed, react with the bromo poly phosphazene; Obtain crosslinked De quaternary phosphine poly phosphazene; After it is dissolved in the organic solvent casting film-forming, use the KOH solution soaking again, promptly obtain the crosslinked alkaline film of poly phosphazene.
6. the preparation of the crosslinked alkaline film of poly phosphazene as claimed in claim 5; It is characterized in that; Described linking agent can be
Figure FSA00000715277000016
(relative molecular mass is in 60～6000 scopes),
Figure FSA00000715277000017
(wherein X can be C, N, O, S),
Figure FSA00000715277000018
(Y wherein can be C, N, q=1～10) or
Figure FSA00000715277000019
(r=2～5).
7. the preparation of a poly phosphazene blend alkalescence film; It is characterized in that, mix polyalcohols in the organic solution with the described quaternary phosphine poly phosphazene of claim 1, mix the organic solution casting film-forming of polyalcohols De quaternary phosphine poly phosphazene after; Use the KOH solution soaking again, promptly obtain poly phosphazene blend alkalescence film.
8. the preparation of poly phosphazene blend alkalescence film as claimed in claim 7; It is characterized in that polyalcohols wherein can be
Figure FSA000007152770000110
(relative molecular mass is in 2.5～300,000 scopes) or
Figure FSA000007152770000111
(relative molecular mass is in 60～6000 scopes).
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105355948A (en) * 2015-11-13 2016-02-24 北京化工大学 Novel polyphosphazene alkaline blend membrane for fuel cell and preparation method thereof
CN106008984A (en) * 2016-06-15 2016-10-12 北京化工大学 Alkaline anion-exchange membrane for fuel cell and preparation method of membrane
CN107204469A (en) * 2017-05-22 2017-09-26 宁波诺丁汉大学 A kind of irreversible temperature response type intelligent battery and preparation method thereof
CN108641090A (en) * 2018-05-17 2018-10-12 北京化工大学 A kind of anion-exchange membrane and preparation method thereof of load cave ether unit
CN112864436A (en) * 2019-11-27 2021-05-28 中国科学院大连化学物理研究所 Fiber-reinforced anion exchange membrane, preparation and application
WO2022186196A1 (en) * 2021-03-02 2022-09-09 株式会社日本触媒 Phosphazene bond-containing polymer

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105355948A (en) * 2015-11-13 2016-02-24 北京化工大学 Novel polyphosphazene alkaline blend membrane for fuel cell and preparation method thereof
CN106008984A (en) * 2016-06-15 2016-10-12 北京化工大学 Alkaline anion-exchange membrane for fuel cell and preparation method of membrane
CN106008984B (en) * 2016-06-15 2021-08-10 北京化工大学 Alkaline anion exchange membrane for fuel cell and preparation method thereof
CN107204469A (en) * 2017-05-22 2017-09-26 宁波诺丁汉大学 A kind of irreversible temperature response type intelligent battery and preparation method thereof
CN107204469B (en) * 2017-05-22 2020-01-07 宁波诺丁汉大学 Reversible temperature response type intelligent battery and preparation method thereof
CN108641090A (en) * 2018-05-17 2018-10-12 北京化工大学 A kind of anion-exchange membrane and preparation method thereof of load cave ether unit
CN108641090B (en) * 2018-05-17 2021-07-20 北京化工大学 Anion exchange membrane loaded with cryptate ether unit and preparation method thereof
CN112864436A (en) * 2019-11-27 2021-05-28 中国科学院大连化学物理研究所 Fiber-reinforced anion exchange membrane, preparation and application
CN112864436B (en) * 2019-11-27 2022-07-12 中国科学院大连化学物理研究所 Fiber-reinforced anion exchange membrane, preparation and application
WO2022186196A1 (en) * 2021-03-02 2022-09-09 株式会社日本触媒 Phosphazene bond-containing polymer

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